A DFT Study Toward The Mechanism of

Articles
A DFT Study toward the Mechanismof

Chromium-Catalyzed Ethylene Trimerization
Werner Janse van Rensburg,*
,
Cronje Grove,
Jan P. Steynberg,
Kl aus B. Stark,
Johan J. Huyser,
and Petrus J. Steynberg*

,
Sasol Technology (Pty) Ltd, R&D Division, 1 KlasieHavenga Road, Sasolburg 9570,
South Africa, Sasol Technology UK, PurdieBuilding, North Haugh St Andrews, Fife,
Scotland, KY16 9ST, and Accelrys I nc., 1042 Kress Street, Houston, Texas 77020
Received October 3, 2003
A theoreti cal study of a mechani sm for ethyl ene tri meri zati on, catal yzed by Cr-pyrrol yl
compl exes, i s proposed and i nvesti gated wi th densi ty functi onal theory methods. The sel ecti ve
formati on of 1-hexene i s general l y accepted to fol l ow a metal l acycl e mechani sm. A detai l ed
spi n state anal ysi s for acti ve speci es i n the mechani sm shows that the tri pl et spi n state
represents the ground spi n state for al l stati onary poi nts. Compl ete Gi bbs free energy (298.15
K) surfaces are mapped for both
5
- and -bondi ng modes of pyrrol e, as wel l as a stri pped-
down Cl ani on model and a ful l Cl Al Me
3
ani on model . From the cal cul ated resul ts i t i s shown
that the proposed metal l acycl e mechani sm i s energeti cal l y favorabl e, wi th metal l acycl e
growth i denti fi ed as the rate-determi ni ng step. I n addi ti on, i t i s demonstrated that di fferent
bondi ng modes of pyrrol e are preferred at di fferent stages i n the proposed mechani sm,
effecti vel y suggesti ng that ri ng sl i ppage of the pyrrol e occurs on the mi ni mum energy path
on the potenti al energy surface. From the cal cul ated resul ts i mportant i nsi ght i s gai ned
i nto the hemi l abi l e nature of the pyrrol e ri ng i n the mechani sm, whi ch i n turn sheds l i ght
on the general requi rements for an effecti ve l i gand i n Cr-catal yzed ethyl ene tri meri zati on.
Introduction
The transi ti on metal catal yzed ol i gomeri zati on of
ethyl ene i s tradi ti onal l y used to synthesi ze R-ol efi ns
wi th product mi xtures usual l y consi sti ng of a mi xture
of even-numbered chai n l engths (C
4
-C
26
).
1
The i mpor-
tance of R-ol efi ns i s real i zed from i ts appl i cati on i n the
producti on of l i near l ow-densi ty pol yethyl ene (LLDPE,
C
6
and C
8
), pl asti ci zer and detergent al cohol s (C
6
-C
16
),
and syntheti c l ubri cants.
2
Sel ecti ve tri meri zati on of
ethyl ene to produce 1-hexene i s hi ghl y desi rabl e because
i t woul d avoi d the producti on of unwanted ol efi ns that
conventi onal transi ti on metal ol i gomeri zati on processes
produce. A l ot of current i nterest i s focused on the
devel opment of homogeneous catal yst systems to sel ec-
ti vel y tri meri ze ethyl ene. Cr-based catal ysts are found
to be especi al l y wel l sui ted for the sel ecti ve tri meri zati on
of ethyl ene, as i s evi dent from a number of l i terature
reports,
3-6
al though Ti ,
7
Ta,
8
and V
9
catal ysi s i s al so
found to have appl i cati on i n thi s area.
Whereas the mechani sm for ethyl ene ol i gomeri zati on
fol l ows the standard Cossee-Arl man coordi nati on/
mi gratory i nserti on mechani sm,
10
the sel ecti ve conver-
si on of ethyl ene to essenti al l y 1-hexene i s attri buted to
* Correspondi ng authors. E-mai l : Werner.JansevanRensburg@sasol .
com; Petri e.Steynberg@sasol .com.
Sasol Technol ogy (Pty) Ltd.
Sasol Technol ogy UK.
Accel rys I nc.

(1) For exampl es, see: (a) Skupi nska, J. Chem. Rev. 1991, 91, 613.
(b) Kei m, W.; Kowal dt, F. H.; Goddard, R.; Kruger, C. Angew. Chem.,
I nt. Ed. Engl. 1978, 17, 466. (c) Svejda, S. A.; Brookhart, M. Organo-
metallics 1999, 18, 65. (d) Ki l l i an, C. M.; Johnson, L. K.; Brookhart,
M. Organometallics 1997, 16, 2005. (e) Mecki ng, S. Coord. Chem. Rev.
2000, 203, 325. (f) Ruther, T.; Braussaud, N.; Cavel l , K. J. Organo-
metallics 2001, 20, 1247. (g) Bri tovsek, G. J. P.; Mastroi anni , S.; Sol an,
G. A.; Baugh, S. P. D.; Redshaw, C.; Gi bson, V. C.; Whi te, A. J. P.;
Wi l l i ams, D. J.; El segood, M. R. J. Chem. Eur. J . 2000, 6, 2221.
(2) Vogt, D. I n Applied Homogeneous Catalysis with Organometallic
Compounds; Corni l s, B., Herrmann, W. A., Eds.; VCH: Wei nhei m,
Germany, 1996; p 245.
(3) (a) Manyi k, R. M.; Wal ker, W. E.; Wi l son, T. P. J . Catal. 1977,
47, 197. (b) Yang, Y.; Ki m, H.; Lee, J.; Pai k, H.; Jang, H. G. Appl. Catal.
A 2000, 193, 29. (c) Wasserschei d, P.; Gri mm, S.; Kohn, R.; Haufe, M.
Adv. Synth. Catal. 2001, 343, 814. (d) Carter, A.; Cohen, S. A.; Cool ey,
N. A.; Murphy, A.; Scutt, J.; Wass, D. F. J . Chem. Soc., Chem. Commun.
2002, 858. (e) Monoi , T.; Sasaki , Y. J . Mol. Catal. A: Chem. 2002, 187,
135. (f) McGui nness, D. S.; Wasserschei d, P.; Kei m, W.; Hu, C.; Engl ert,
U.; Di xon, J. T.; Grove, C. J . Chem. Soc., Chem. Commun. 2003, 334.
(g) McGui nness, D. S.; Wasserschei d, P.; Kei m, W.; Morgan, D.; Di xon,
J. T.; Bol l mann, A.; Maumel a, H.; Hess, F.; Engl ert, U. J . Am. Chem.
Soc. 2003, 125, 5272. (h) Morgan, D. H.; Schwi kkard, S. L.; Di xon, J.
T.; Nai r, J. J.; Hunter, R. Adv. Synth. Catal. 2003, 939. (i ) Commereuc,
D.; Drochon, S.; Saussi ne, L. (I nsti tut Francai s du Petrol e) US Patent
6031145, 2000. (j) Wu, F.-J. (Amoco Corp.) US Patent 5811618, 1998.
(k) Aoyama, T.; Mi mura, H.; Yamamoto, T.; Oguri , M.; Koi e, Y. (Tosoh
Corp.) JP Patent 09176229, 1997.
(4) Bri ggs, J. R. J . Chem. Soc., Chem. Commun. 1989, 674.
(5) (a) Reagan, W. K.; Petti john, T. M.; Freeman, J. W.; Benham,
E. A. (Phi l l i ps Petrol eum Co.)US Patent 5786431, 1998. (b) Lashi er,
M. E. (Phi l l i ps Petrol eum Co.) EP 0780353A1, 1997.
(6) (a) Jol l y, P. W. Acc. Chem. Res. 1996, 29, 544. (b) Emri ch, R.;
Hei nemann, O.; Jol l y, P. W.; Kruger, C.; Verhovni k, G. P. J. Organo-
metallics 1997, 16, 1511.
1207 Organometallics 2004, 23, 1207-1222
10.1021/om0306269 CCC: $27.50 2004 Ameri can Chemi cal Soci ety
Publ i cati on on Web 02/17/2004
metal l acycl e i ntermedi ates.
4,6
Very recentl y proposed
metal l acycl e mechani sms for Ti -
11
and Ta-catal yzed
12
ethyl ene tri meri zati on were i nvesti gated wi th hi gh-l evel
densi ty functi onal theory (DFT). To the best of our
knowl edge, however, no theoreti cal study of a possi bl e
Cr-catal yzed mechani sm for ethyl ene tri meri zati on has
yet been reported. Thi s i s attri buted to the l ack of
avai l abl e fundamental experi mental data on both the
exact nature of Cr speci es i n the catal yti c cycl e and the
el ectroni c structure of Cr compl exes whi ch requi re
notori ousl y chal l engi ng open shel l cal cul ati ons.
I n the present paper we propose and i nvesti gate an
ethyl ene tri meri zati on mechani sm based on Cr-pyrrol yl
compl exes, whi ch represents one of the most successful
ethyl ene tri meri zati on systems known (Phi l l i ps Petro-
l eum Company).
5
Experi mental l y i t i s found that the
combi nati on of chromi um tri (ethyl hexanoate) [Cr(EH)
3
],
di methyl pyrrol e, tri ethyl al umi num, and di ethyl al umi -
num chl ori de yi el ds a hi ghl y reacti ve ethyl ene tri mer-
i zati on system.
5
The proposed mechani sm for ethyl ene
tri meri zati on wi th a pyrrol e-based system i s i l l ustrated
i n Fi gure 1.
4,6
Catal yst i ni ti ati on i s proposed to i nvol ve deprotona-
ti on of the pyrrol e l i gand, one-el ectron i nner shel l
reducti on of the Cr(I I I ) i n Cr(EH)
3
, l i gand exchange,
ani on formati on, and coordi nati on of two ethyl ene
mol ecul es to yi el d the neutral Cr(I I ) speci es, 1, as the
fi rst acti ve i ntermedi ate i n the catal yti c cycl e. Al kyl a-
l umi num (TEA) acti vati on of the Cr(I I I ) catal yst precur-
sor i s bel i eved to i nvol ve homol yti c cl eavage of a Cr-O
bond through i nteracti on of Al wi th the carbonyl oxygen
of an ethyl hexanoate fragment, as presented schemati -
cal l y i n Fi gure 2. From thi s one-el ectron i nner shel l
reducti on process an acti ve Cr(I I ) speci es i s generated
together wi th a correspondi ng ethane radi cal .
13
A
si mi l ar Cr(I I I ) acti vati on process i nvol vi ng i nteracti on
of Cr(EH)
3
wi th TEA, i n the presence of an al ternati ve
l i gand (2,6-di phenyl phenol /ani sol e), i s suggested i n a
very recent report by Morgan et al .
3h
I n thei r work
magneti c suscepti bi l i ty measurements on the acti vated
catal yst system showed
eff
val ues of 5.17 and 3.61
B
i n xyl ene and tol uene, respecti vel y, i ndi cati ve of Cr(I I )
speci es. Thi s effecti vel y supports the suggesti on that
Cr(I I ) i ntermedi ates account for the i ni ti al acti vated
catal yti c speci es.
The ani on fragment of 1 i s proposed to consi st of a
Cl Al Et
3
uni t, or ol i gomer thereof,
3b
whi ch remai ns
coordi nated throughout the mechani sti c cycl e. Metal -
l acycl e formati on from 1i nvol ves oxi dati ve addi ti on of
the two ethyl ene fragments to yi el d a fi ve-membered
Cr(I V) metal l acycl e, 2. Thi s i s fol l owed by the coordi na-
ti on of a thi rd ethyl ene mol ecul e to yi el d 3. Subsequent
metal l acycl e growth resul ts from i nserti on of the thi rd
ethyl ene mol ecul e i nto the fi ve-membered metal l acycl i c
ri ng to yi el d the seven-membered metal l acycl e speci es
4. The precedence for fi ve- and seven-membered Cr
metal l acycl es has been establ i shed by the i sol ati on and
characteri zati on of crystal structures on rel ated com-
pl exes.
6,14
1-Hexene l i berati on i s afforded by reducti ve
el i mi nati ve i ntramol ecul ar -hydrogen mi grati on to the
-carbon and regenerati on of the acti ve catal yti c Cr(I I )
speci es, 1, upon coordi nati on of two ethyl ene mol ecul es.
I n thi s theoreti cal study hi gh-l evel densi ty functi onal
theory i s used to assess the val i di ty of the proposed
mechani sm (Fi gure 1). Al though a number of assump-
ti ons wi th regard to the mechani sm are made, e.g., the
presence of Cr(I I ) and Cr(I V) as acti ve speci es i n the
mechani sm and nature of the ani oni c fragment, i t i s
bel i eved that the proposed mechani sm represents an
acceptabl e hypothesi s sui tabl e as a thorough fi rst at-
tempt to theoreti cal l y i nvesti gate a Cr-catal yzed ethyl -
ene tri meri zati on mechani sm. I n addi ti on to the map-
pi ng of the potenti al energy surface (PES) of the
proposed mechani sm a number of addi ti onal fundamen-
tal aspects are al so addressed, e.g., the preferred spi n
state of vari ous Cr speci es, the i nfl uence of coordi nati on
mode of the pyrrol e l i gand, nature of the ani oni c
(7) (a) Deckers, P. J. W.; Hessen, B.; Teuben, J. H. Angew. Chem.,
I nt. Ed. 2001, 40, 2516. (b) Deckers, P. J. W.; Hessen, B.; Teuben, J.
H. Organometallics 2002, 21, 5122. (c) Pel l echi a, C.; Pappal ardo, D.;
Ol i va, L.; Mazzeo, M.; Gruter, G.-J. Macromolecules 2000, 33, 2807.
(8) Andes, C.; Harki ns, S. B.; Murtuza, S.; Oyl er, K.; Sen, A. J . Am.
Chem. Soc. 2001, 123, 7423.
(9) Santi , R.; Romano, A. M.; Grande, M.; Sommazzi , A.; Masi , F.;
Proto, A. (ENI CHEM S.P.A.) WO 0168572, 2001.
(10) (a) Cossee, P. J . Catal. 1964, 3, 80. (b) Arl man, E. J.; Cossee,
P. J . Catal. 1964, 3, 99.
(11) (a) Bl ok, A. N. J.; Budzel aar, P. H. M.; Gal , A. W. Organome-
tallics 2003, 22, 2564. (b) de Brui n, T. J. M.; Magna, L.; Raybaud, P.;
Toul hout, H. Organometallics 2003, 22, 3404.
(12) Yu, Z.-X.; Houk, K. N. Angew. Chem., I nt. Ed. 2003, 42, 808.
(13) From unpubl i shed i n-house experi mental studi es on the Cr-
pyrrol yl catal yst system the fol l owi ng observati ons are made for
catal yst acti vati on: (i ) Duri ng TEA/Cr(EH)3 catal yst acti vati on a
gaseous whi te haze i s observed as part of the reacti on mi xture.
Al though not anal yzed as such, i t i s strongl y bel i eved that thi s
observati on i s expl ai ned by the formati on of butane gas resul ti ng from
the coordi nati on of two ethane radi cal speci es, whi ch i s i n turn formed
duri ng the acti vati on process. (i i ) Duri ng acti vati on a di sti nct col or
change from green to brown i s observed, i n l i ne wi th a Cr(I I I ) to Cr-
(I I ) oxi dati on state change.
(14) Bercaw, J. E. The 15th I nternati onal Symposi um on Ol efi n
Metathesi s and Rel ated Chemi stry (I SOM XV) Jul y 28-Aug 1, 2003,
Kyoto, Japan.
Figure 1. Proposed metal l acycl e mechani sm for Cr-
pyrrol yl -catal yzed tri meri zati on of ethyl ene.
Figure 2. Proposed mechani sm for Cr(I I I ) acti vati on by
TEA.
1208 Organometallics, Vol. 23, No. 6, 2004 J ansevan Rensburg et al.
fragment, conformati ons of the metal l acycl e ri ngs, and
charge di stri buti on effects.
Computational Details
For most equi l i bri um structures prel i mi nary geometri es
were opti mi zed by usi ng the PM3
15
semi empi ri cal Hami l toni an
avai l abl e i n Spartan02 (Wavefuncti on I nc.).
16
Thi s approach
ensured the rapi d scanni ng of the prel i mi nary PES and
provi ded reasonabl e starti ng geometri es for hi gher l evel DFT
cal cul ati ons. Al l fi nal geometry opti mi zati ons were performed
wi th the DMol
3
densi ty functi onal theory (DFT) code
17
as
i mpl emented i n the Materi al sStudi o (Versi on 2.1.5) program
package of Accel rys I nc. The nonl ocal general i zed gradi ent
approxi mati on (GGA) functi onal by Perdew and Wang (PW91)
18
was used for al l geometry opti mi zati ons. The convergence
cri teri a for these opti mi zati ons consi sted of threshol d val ues
of 2 10
-5
Ha, 0.00189 Ha/, and 0.00529 for energy,
gradi ent, and di spl acement convergence, respecti vel y, whi l e
a sel f-consi stent-fi el d (SCF) densi ty convergence threshol d
val ue of 1 10
-6
Ha was speci fi ed. DMol
3
uti l i zes a basi s set
of numeri c atomi c functi ons, whi ch are exact sol uti ons to the
Kohn-Sham equati ons for the atoms.
19
These basi s sets are
general l y more compl ete than a comparabl e set of l i nearl y
i ndependent Gaussi an functi ons and have been demonstrated
to have smal l basi s set superposi ti on errors.
19
I n the present
study a pol ari zed spl i t val ence basi s set, termed doubl e
numeri c pol ari zed (DNP) basi s set, has been used. Al l geometry
opti mi zati ons empl oyed hi ghl y effi ci ent del ocal i zed i nternal
coordi nates.
20
The use of del ocal i zed coordi nates si gni fi cantl y
reduces the number of geometry opti mi zati on i terati ons needed
to opti mi ze l arger mol ecul es compared to the use of tradi ti onal
Cartesi an coordi nates.
Al l the geometri es opti mi zed were al so subjected to ful l
frequency anal yses at the same GGA/PW91/DNP l evel of
theory to veri fy the nature of al l stati onary poi nts. Equi l i bri um
geometri es were characteri zed by the absence of i magi nary
frequenci es. Prel i mi nary transi ti on state geometri es were
obtai ned by ei ther the DMol
3
PES scan functi onal i ty i n Ceri us
2
(Versi on 4.8, Accel rys, I nc.) or the i ntegrated l i near synchro-
nous transi t/quadrati c synchronous transi t (LST/QST) al go-
ri thm
21
avai l abl e i n Materi al sStudi o. These prel i mi nary struc-
tures were then subjected to ful l TS opti mi zati ons usi ng an
ei genvector fol l owi ng al gori thm. For sel ected transi ti on state
geometri es confi rmati on cal cul ati ons, i nvol vi ng i ntri nsi c reac-
ti on path (I RP)
22
cal cul ati ons, were performed i n whi ch the
path connecti ng reagent, TS, and product are mapped. The
I RP cal cul ati ons, performed at the same GGA/PW91/DNP l evel
of theory, ensured the di rect connecti on of transi ti on states
wi th the respecti ve reactant and product geometri es. Al l I RP
cal cul ati ons performed are referred to i n the text. Al l transi ti on
structure geometri es exhi bi ted onl y one i magi nary frequency
i n the reacti on coordi nate. Al l reported energi es refer to Gi bbs
free energy correcti ons to the total el ectroni c energi es at 298.15
K wi th the i ncl usi on of zero-poi nt energy (ZPE) correcti ons,
unl ess expl i ci tl y stated to the contrary.
A comprehensi ve anal ysi s of preferred mul ti pl i ci ty of Cr for
sel ected Cr(I I ) and Cr(I V) compl exes, i ncl udi ng representati ve
exampl es for both equi l i bri um and transi ti on state geometri es,
was performed by conducti ng open shel l cal cul ati ons for
el ectrons i n the exci ted states. For si ngl et structures cl osed
shel l opti mi zati ons were performed. The three possi bl e spi n
states of Cr(I I ) compl exes (si ngl et, tri pl et, and qui ntet) and
two spi n states for Cr(I V) compl exes (si ngl et and tri pl et) were
consi dered. From thi s anal ysi s (di scussed i n detai l i n the
Resul ts and Di scussi on secti on) a preferred tri pl et spi n state
for stati onary poi nts i n the proposed mechani sti c cycl e (con-
si sti ng of onl y Cr(I I ) and Cr(I V) speci es) was establ i shed, i n
agreement wi th the tendency of Cr to exhi bi t hi gh spi n states.
Consequentl y, unrestri cted tri pl et spi n states were speci fi ed
for al l geometry opti mi zati ons unl ess expl i ci tl y stated to the
contrary.
Sel f-consi stent-fi el d (SCF) convergence probl ems are fre-
quentl y encountered for open shel l organometal l i c systems. To
enhance SCF convergence effi ci ency duri ng opti mi zati on of
stati onary poi nts, a smal l el ectron thermal smeari ng val ue of
0.005 Ha was speci fi ed for al l cal cul ati ons unl ess expl i ci tl y
stated to the contrary. The thermal smeari ng opti on i n
Materi al sStudi o makes use of a fracti onal el ectron occupancy
scheme at the Fermi l evel accordi ng to a fi ni te-temperature
Fermi functi on.
23,24
The appl i cati on of thi s techni que was
justi fi ed by the rel ati vel y si mi l ar energy di fferences and
geometri es obtai ned for reference cal cul ati ons i n whi ch smear-
i ng and no smeari ng were used. Popul ati on anal ysi s (Hi rshfel d
charges) was performed for GGA/PW91/DNP opti mi zed struc-
tures at the same l evel of theory.
25
Results and Discussion
LigandCoordinationMode. Throughout thi s study
pyrrol e i s used as model l i gand for 2,5-di methyl pyrrol e
commonl y used i n experi mental studi es.
26
Pyrrol e can
theoreti cal l y coordi nate i n a number of ways to a metal
center, i ncl udi ng pentahapto (
5
), tri hapto (
3
), and
si gma () bondi ng (wi th a coval ent Cr-N i nteracti on)
modes. I n the
5
-bondi ng mode the l i gand acts as a
tri dentate l i gand, contri buti ng si x el ectrons to the
coordi nati on sphere of Cr, whi l e the -bondi ng mode i s
monodentate, contri buti ng onl y two el ectrons to the
val ence shel l . Therefore, speci es 1and 3i n Fi gure 1 are
16-el ectron compl exes for
5
-pyrrol e and 12-el ectron
compl exes for -pyrrol e, whereas 2 and 4 i n Fi gure 1
are 14-el ectron compl exes for
5
-pyrrol e and 10-el ectron
compl exes for -pyrrol e. I t i s thus evi dent that the
bondi ng mode of pyrrol e wi l l di ctate the val ence el ectron
count i n the acti ve catal yti c speci es. For al l compl exes
opti mi zed i n thi s study the
5
- and -bondi ng modes of
pyrrol e, whi ch represents the two most l i kel y extremes
for bondi ng of pyrrol e,
27
were expl i ci tl y consi dered to
assess the preferred l i gand bondi ng modes of the
rel evant compl exes.
(15) Stewart, J. J. P. J . Comput. Chem. 1989, 10, 209.
(16) Wavefuncti on, I nc.: 18401 Von Karman Avenue, Sui te 370,
I rvi ne, CA 92612.
(17) (a) Del l ey, B. J . Chem. Phys. 1990, 92, 508. (b) Del l ey, B. J .
Phys. Chem. 1996, 100, 6107. (c) Del l ey, B. J . Chem. Phys. 2000, 113,
7756.
(18) Perdew, J. P.; Wang, Y. Phys. Rev. 1992, B45, 13244.
(19) Del l ey, B. Density Functional Theory: A Tool for Chemistry;
Semi nari o, J. M., Pol i tzer, P., Eds.; El sevi er: Amsterdam, The
Netherl ands, 1995.
(20) Andzel m, J.; Ki ng-Smi th, R. D.; Fi tzgeral d, G. Chem. Phys. Lett.
2001, 335, 321.
(21) Govi nd, N.; Petersen, M.; Fi tzgeral d, G.; Ki ng-Smi th, D.;
Andzel m, J. Comput. Mater. Sci. (accepted for publ i cati on).
(22) The I RP techni que used i n Materi al sStudi o (Accel rys I nc.,
Versi on 2.1.5) al so corresponds to the i ntui ti ve mi ni mum energy
pathway (MEP) connecti ng two structures and i s based on the nudged-
el asti c band (NEB) al gori thm of Henkel man and Jonsson: Henkel man,
G.; Jonsson, H. J . Chem. Phys. 2000, 113, 9978.
(23) Del l ey, B. I n Modern Density Functional Theory: A Tool for
Chemistry; Semi nari o, J. M., Pol i tzer, P., Eds.; Theoreti cal and
Computati onal Chemi stry, Vol . 2, El sevi er: Amsterdam, The Neth-
erl ands, 1995.
(24) Wei nert, M.; Davenport, J. W. Phys. Rev. B 1992, 45, 13709.
(25) (a) Hi rshfel d, F. L. Theor. Chim. Acta B 1977, 44, 129. (b)
Del l ey, B. Chem. Phys. Lett. 1986, 110, 329.
(26) I t was found from i n-house experi mental studi es that ethyl ene
tri meri zatri ti on runs wi th pyrrol e as l i gand behave si mi l arl y compared
to 2,5-di methyl pyrrol e.
(27) Reagan, W. K. Symposi um on novel preparati on and conversi on
of l i ght ol efi ns presented before the Di vi si on of Petrol eum Chemi stry,
I nc., Ameri can Chemi cal Soci ety, Mi ami Beach meeti ng, Sept 10-15,
1989.
Chromium-Catalyzed EthyleneTrimerization Organometallics, Vol. 23, No. 6, 2004 1209
Multiplicity. Coordi nati on compounds contai ni ng
soft -aci di c l i gands (e.g., Cp-, pyrrol e-ani ons, etc.) are
often found i n l ow oxi dati on states, where the strongl y
coval ent metal -l i gand i nteracti ons typi cal l y enforce the
18-el ectron rul e and a spi n-pai red ground state. Cr(0),
wi th i ts 3d
5
4s
1
val ence shel l , as wel l as the di fferent
oxi dati on states of Cr (Cr
1+
-Cr
5+
), exhi bi t unpai red
el ectrons i n the val ence shel l , and the associ ated
paramagneti sm makes NMR characteri zati on of Cr
compl exes i mpracti cal . Organometal l i c compl exes of thi s
nature, someti mes al so referred to as metal l aradi cal s,
are notori ousl y di ffi cul t to accommodate computati on-
al l y due to SCF convergence probl ems often encoun-
tered, as wel l as the computati onal l y expensi ve nature
of open shel l cal cul ati ons. These phenomena are prob-
abl y the reasons that theoreti cal studi es based on Cr
chemi stry are l ess frequentl y encountered compared to
other transi ti on metal s.
The rel evance of el ectron pai ri ng energy as a possi bl e
destabi l i zi ng factor for l i gand coordi nati on to Cr was
addressed i n open shel l computati onal studi es (MP2 and
DFT) by Cacel l i et al .
28
I n thei r work i t was poi nted out
that i n the presence of an addi ti onal PH
3
donor, whi ch
wi l l exert a favorabl e chel ate effect, 22.5 kcal /mol i s
needed to promote the quartet ground state 15-el ectron
compl ex, CpCr
(I I I )
Cl
2
(PH
3
), to the doubl et exci ted state
(i .e., vacati ng a si ngl y occupi ed val ence shel l orbi tal ),
whi l e onl y 16.5 kcal /mol i s gai ned upon formati on of the
doubl et 17-el ectron compl ex, CpCr
(I I I )
Cl
2
(PH
3
)
2
, from the
doubl et 15-el ectron precursor, CpCr
(I I I )
Cl
2
(PH
3
). Thi s
shows that the energy gai ned upon donor l i gand coor-
di nati on i s not suffi ci ent to overcome the el ectron
pai ri ng energy of the Cr(I I I ) center. I n more recent
cal cul ati ons
29
the i mportance of spi n state crossi ng
duri ng the reacti on of transi ti on metal compounds i s
emphasi zed. These spi n crossi ng phenomena are al so
referred to as two-state reacti vi ty (TSR)
30
i nvol vi ng
parti ci pati on of spi n i nversi on at transi ti on states. From
these studi es i t i s cl ear that consi derati on of al l possi bl e
spi n states of a transi ti on metal center i s essenti al to
ensure that when spi n state crossi ng does occur, the
mi ni mum energy crossi ng poi nt (MECP) has been
obtai ned. MECPs are parti cul arl y i mportant when
equi l i bri um structures for reagents and products have
di fferent spi n states and when transi ti on state geom-
etri es exhi bi t di fferent spi n states, on the l owest energy
path, compared to reagents and/or products. Obtai ni ng
experi mental evi dence for spi n state crossi ngs woul d
requi re spi n state measurements of i ntermedi ates, a
chal l engi ng
29
aspect that has not been conducted suc-
cessful l y yet. Therefore, spi n state crossi ngs are more
conveni entl y addressed by a computati onal approach.
29,30
From these studi es i t was observed that the nature of
the exchange part of the DFT functi onal strongl y
i nfl uences the accuracy of the computed spi n state
spl i tti ngs, whi ch i s parti cul arl y strong for the fi rst-row
transi ti on metal s (Sc-Cu) wi th presumabl y l arge ex-
change i nteracti ons between the compact 3d orbi tal s of
these metal s. Consequentl y, the i denti fi cati on of the
ground spi n states for the di fferent Cr(I I ) and Cr(I V)
equi l i bri um and transi ti on state geometri es i n our study
i s essenti al to ensure the l ocati on of the l owest energy
stati onary poi nts on the cal cul ated PESs. Currentl y,
methodol ogy to accuratel y compute MECP energi es for
open shel l transi ti on metal compl exes i s not avai l abl e
i n Materi al sStudi o (see Computati onal Detai l s), and we
have opted for a manual approach to determi ne whether
Cr spi n state i s conserved or al tered duri ng the catal yti c
cycl e. Fi ve model stati onary poi nts i n the proposed
mechani sti c cycl e (Fi gure 1) were i denti fi ed as repre-
sentati ve structures for the spi n state anal ysi s, vi z., the
Cr(I I ) ethyl ene coordi nati on compl ex (M1), the Cr(I V)
fi ve-membered metal l acycl e (M2), the di rect Cr(I V)
seven-membered metal l acycl e product (M3), the transi -
ti on structure for metal l acycl e formati on (M1-2), and
the transi ti on structure for metal l acycl e growth (M2-
3), i l l ustrated i n Fi gure 3.
The sel ected transi ti on state geometri es represent
exampl es of both a change of oxi dati on state of Cr [from
Cr(I I ) to Cr(I V), M1-2] and conservati on of oxi dati on
state of Cr [(Cr(I V), M2-3] duri ng the respecti ve
transformati ons. Both
5
- and -bondi ng modes of
pyrrol e were expl i ci tl y consi dered for al l fi ve geometri es.
For the Cr(I I ) compl exes, M1 and M1-2, three spi n
states (si ngl et, tri pl et, and qui ntet) were consi dered,
whi l e two spi n states (si ngl et and tri pl et) were consi d-
ered for the Cr(I V) speci es, M2, M2-3, and M3, ef-
fecti vel y representi ng al l possi bl e mul ti pl i ci ti es. Ful l
equi l i bri um and transi ti on state geometry opti mi zati ons
were performed both wi thout fracti onal occupati on (no
smeari ng) of orbi tal s at the Fermi l evel and wi th
speci fyi ng a thermal smeari ng range of 0.005 Ha to yi el d
a total of 48 geometry opti mi zati ons.
31
The rel ati ve
cal cul ated el ectroni c energi es for the di fferent spi n
states of these opti mi zed geometri es are summari zed
i n Tabl e 1.
From the rel ati ve val ues i n Tabl e 1 i t i s evi dent that
the tri pl et spi n state represents the ground state for al l
equi l i bri um and transi ti on state geometri es consi dered.
No structure for
5
-pyrrol e qui ntet M1coul d successful l y
be opti mi zed i n whi ch i t was found that both ethyl ene
mol ecul es spontaneousl y dri ft away from the Cr center
duri ng opti mi zati on. Thi s resul t i s not surpri si ng si nce
the number of avai l abl e coordi nati on si tes i n
5
-pyrrol e
M1i s exceeded by 1 (assumi ng a preferred octahedral
6 si te arrangement) i n the hi gh qui ntet spi n state,
effecti vel y el i mi nati ng the possi bi l i ty for the proposed
structure to exi st. The smal l est di fference i n rel ati ve
spi n state energi es i s found for the -pyrrol e M1
geometry i n whi ch the si ngl et structure i s 2.9 kcal /mol
(28) (a) Cacel l i , I .; Keogh, D. W.; Pol i , R.; Ri zzo, A. New J . Chem.
1997, 21, 133. (b) Cacel l i , I .; Keogh, D. W.; Pol i , R.; Ri zzo, A. J . Phys.
Chem. A 1997, 101, 9801.
(29) (a) Pol i , R.; Harvey, J. N. Chem. Soc. Rev. 2003, 32, 1. (b) Green,
J. C.; Harvey, J. N.; Pol i , R. J . Chem. Soc., Dalton Trans. 2002, 1861.
(c) Harvey, J. N.; Aschi , M.; Schwarz, H.; Koch, W. Theor. Chem. Acc.
1998, 99, 95.
(30) Schroder, D.; Shai k, S.; Schwarz, H. Acc. Chem. Res. 2000, 33,
139.
(31) Al though not al l uded to here, subtl e di fferences i n geometri cal
parameters for compl exes opti mi zed at di fferent spi n states were found.
Coordi nates for al l these geometri es opti mi zed at di fferent spi n states
are i ncl uded i n the Supporti ng I nformati on.
Figure 3. Equi l i bri um and transi ti on state geometri es
consi dered i n mul ti pl i ci ty anal ysi s.
hi gher and the qui ntet structure 3.5 kcal /mol hi gher i n
energy compared to the tri pl et geometry. I n al l the other
cases the al ternati ve spi n states were si gni fi cantl y
hi gher i n energy (10.6-25.9 kcal /mol ) compared to the
preferred tri pl et geometri es. Rel ati ve energi es obtai ned
for the qui ntet transi ti on structures, M1-2, were found
to be si gni fi cantl y hi gher i n energy compared to both
the si ngl et and tri pl et opti mi zed geometri es, effecti vel y
showi ng that the hi ghest spi n state does not necessari l y
represent the most favored spi n state for Cr compl exes.
Geometry opti mi zati ons for the si ngl et -pyrrol e com-
pl ex M3and the qui ntet -pyrrol e transi ti on structure
M1-2, as i ndi cated i n Tabl e 1, coul d not successful l y
be opti mi zed when i nteger val ues for orbi tal occupati ons
of el ectrons at the Fermi l evel (no smeari ng) were
enforced. I n both cases the SCF i terati ons di d not
converge. However, i t i s evi dent from the rel ati ve
energi es cal cul ated for fracti onal el ectron occupati on at
the Fermi l evel (0.005 Ha smeari ng) that the tri pl et spi n
state prevai l s as ground state throughout. A general
compari son of rel ati ve spi n state energi es cal cul ated for
al l speci es i n Tabl e 1 shows that essenti al l y smal l
di fferences are found between rel ati ve energi es obtai ned
wi th (0.005 Ha) and wi thout smeari ng. From thi s
mul ti pl i ci ty anal ysi s we thus concl ude that i n our study
a tri pl et spi n state i s conserved throughout the proposed
mechani sti c cycl e. Furthermore, the use of a thermal
smeari ng range of 0.005 Ha was found to yi el d energy
di fferences si mi l ar to the energi es where no smeari ng
was speci fi ed, effecti vel y prompti ng the use of thermal
smeari ng for al l geometry opti mi zati ons di scussed i n the
remai nder of thi s paper. Thi s strategy ensured the
effi ci ent convergence of SCF i terati ons for al l geometry
opti mi zati ons conducted.
Geometries. For the cal cul ated ethyl ene tri meri za-
ti on mechani sti c cycl e two bondi ng modes of the pyrrol e
l i gand are expl i ci tl y consi dered for al l opti mi zed geom-
etri es, vi z., a
5
- and -bonded pyrrol e. I n addi ti on, a
stri pped-down model , consi sti ng of onl y a Cl atom as
ani oni c fragment, and a ful l model , consi sti ng of Cl A-
l Me
3
as ani on, are i nvesti gated for both bondi ng modes
of pyrrol e. Geometri es for the Cl model s wi l l be desi g-
nated as Hx and Sx for the respecti ve
5
- and -bondi ng
modes of pyrrol e, whi l e the desi gnati ons Hx and Sx
wi l l be used for the Cl Al Me
3
model s. I n thi s secti on the
geometri cal resul ts obtai ned for the Cl model s wi l l be
presented fi rst, fol l owed by a bri ef compari son of di f-
ferences i n geometri es obtai ned upon changi ng from the
Cl model to the ful l Cl Al Me
3
model .
The opti mi zed geometri es for
5
-bonded pyrrol e (Cl
model ) parti ci pati ng i n the proposed ethyl ene tri mer-
i zati on mechani sm are i l l ustrated i n Fi gure 4, whi l e the
correspondi ng -bonded pyrrol e geometri es are i l l us-
trated i n Fi gure 5. The Cr(I I ) speci es H1i s consi dered
as the fi rst acti ve i ntermedi ate i n the tri meri zati on
cycl e. The opti mi zed structure exhi bi ts tetrahedral
geometry wi th Cr-Py and Cr-Cl di stances of 1.927 and
2.266 , respecti vel y. The Cr center i s i n the pl ane
defi ned by the four carbon atoms of the bonded ethyl ene
mol ecul es, and each ethyl ene mol ecul e i s weakl y coor-
di nated to Cr vi a -bondi ng i nteracti on. The rel ati vel y
weak nature of the -bondi ng i s refl ected i n the rel a-
ti vel y short C-C bond di stance of 1.381 , whi ch i s onl y
0.045 l onger than the cal cul ated CdC di stance i n free
ethyl ene. Furthermore, the Cr-C di stances for a si ngl e
ethyl ene fragment i s not symmetri cal , 2.245 and 2.331
, respecti vel y, wi th the carbon atom desi gnated for
coupl i ng wi th the other ethyl ene fragment exhi bi ti ng
the l ongest Cr-C di stance. The cal cul ated Cr-N di s-
tance i n S1i s 1.904 , and the Cl l i gand, as wel l as the
two ethyl ene fragments, i s more ti ghtl y coordi nated to
Cr compared to H1. Thi s rel ati vel y contracted nature
of the l i gands i s attri buted to a hi gher demand for
el ectron densi ty by Cr when pyrrol e i s bonded i n a
-mode, i n accord wi th the coordi nati vel y unsaturated
nature of Cr for -pyrrol e (vi de i nfra). Another si gni fi -
cant di fference i n the geometri es of H1 and S1 i s the
more pronounced pi ano-stool geometry for the former,
i n whi ch the Cl and ethyl ene fragments are bent away
from the pyrrol e l i gand.
Formati on of the fi ve-membered metal l acycl e Cr(I V)
speci es H2i s afforded by oxi dati ve addi ti on of the two
ethyl ene fragments vi a the transi ti on structure H1-2.
I n H1-2the coupl i ng C-C di stance i s decreased from
2.598 i n H1 to 1.898 , whi l e contracti on of the
5
-
bonded pyrrol e ri ng i n the transi ti on state i s evi dent
from the changes i n Cr-Py di stance from 1.927 f
1.912 f 1.968 i n the sequence H1f H1-2f H2.
The transi ti on structure for metal l acycl e formati on of
the -bonded pyrrol e model , S1-2, poi nts to a si gni fi -
cantl y earl i er transi ti on state, as i s evi dent from the
rel ati vel y l onger C-C coupl i ng di stance (2.034 ) and
l arger C-Cr-C angl e (123.4) compared to H1-2. The
fi ve-membered metal l acycl e products, H2and S2, have
C-C coupl i ng di stances of 1.529 and 1.536 , respec-
ti vel y, whi ch i s i n agreement wi th the expected di stance
for C-C si ngl e bonds. For both H2 and S2 the Cr-Cl
and Cr-Py di stances are shorter for the Cr(I V) com-
pl exes compared to the di stances obtai ned for the Cr(I I )
compl exes H1 and S1.
I n order for ethyl ene tri meri zati on to proceed, the
i ncorporati on of a thi rd ethyl ene mol ecul e i s necessary.
I nteracti on of ethyl ene wi th the fi ve-membered metal -
l acycl e H2affords H3, i n whi ch the ethyl ene fragment
i s weakl y coordi nated vi a a l ong-range -i nteracti on.
Thi s i s evi dent from the el ongated Cr-C di stances
Table 1. Relative Electronic Energies for Different Spin States of M1, M1-2, M2, M2-3, and M3 in kcal/mol
(values in parentheses are calculated with a thermal smearing range of 0.005 Ha)
M1 M1-2 M2 M2-3 M3
5
-pyrrol e si ngl et 16.4 (15.1) 9.9 (9.3) 15.2 (14.1) 17.1 (14.9) 12.2 (11.5)
tri pl et 0.0 (0.0) 0.0 (0.0) 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
qui ntet a 25.9 (25.9)
-pyrrol e si ngl et 2.9 (2.9) 15.7 (11.5) 19.4 (17.8) 10.6 (10.5) b(15.7)
tri pl et 0.0 (0.0) 0.0 (0.0) 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
qui ntet 3.5 (3.4) b (22.0)
a
No structure coul d successful l y be opti mi zed for qui ntet M1 due to the l ack of suffi ci ent coordi nati on si tes on Cr(I I ) i n the hi ghest
qui ntet spi n state. I n al l efforts both ethyl ene mol ecul es spontaneousl y dri fted away from the Cr center.
b
SCF di d not converge when no
smeari ng was speci fi ed.
(2.464 and 2.586 ) for Cr-ethyl ene i n H3, as wel l as
the rel ati vel y short CdC di stance of 1.355 for the
coordi nated ethyl ene fragment. The si gni fi cantl y en-
dothermi c nature (vi de i nfra) of ethyl ene coordi nati on
to H2, to yi el d the 16-el ectron speci es H3, corroborates
the fact that Cr compl exes tend to favor a l ow el ectron
count i n the val ence shel l . Thi s i s al so evi dent from
unsuccessful efforts to opti mi ze a geometry si mi l ar to
H3 for -bonded pyrrol e; each attempt l ed to the
spontaneous di ssoci ati on of ethyl ene from the 10-
el ectron speci es, S2, duri ng opti mi zati on. I t i s therefore
proposed that H3represents a shal l ow l ocal mi ni mum
on the PES for effecti ve concerted metal l acycl e growth
from H2 to H4. I nserti on of the coordi nated ethyl ene
fragment i nto the Cr-C3 bond, and not the Cr-C6
bond, of H3 i s suggested from the el ongated nature of
Cr-C3 (2.177 ) compared to Cr-C6 (2.137 ). Metal -
l acycl e growth (H3f H3-4f H4) to yi el d the seven-
membered metal l acycl e, H4, proceeds by i nserti on of
ethyl ene i nto the Cr-C3 bond vi a the transi ti on struc-
ture H3-4. I n H3-4formati on of the Cr-C1 (2.196 )
and C2-C3 (2.243 ) bonds and rupture of the Cr-C3
(2.362 ) bond and C1-C2 (1.406 ) -bond proceed i n
a concerted fashi on. I n H4 the Cr-C1 bond rel axes to
2.058 . A transi ti on structure si mi l ar to H3-4 was
successful l y opti mi zed for a -bonded pyrrol e compl ex
(S3-4). I n S3-4the C2-C3 di stance (2.279 ) i s found
to be si mi l ar compared to H3-4, whi l e the Cr-C3
di stance (2.181 ) i s si gni fi cantl y shorter and ac-
compani ed by an agosti c i nteracti on (2.012 ) between
Cr and a hydrogen on C3, whi ch i s not observed for H3-
4. Thi s addi ti onal bondi ng i nteracti on found for the
-bonded model refl ects a comparati ve l ack of el ectron
densi ty at the metal center i n the transi ti on state, whi ch
i s not necessari l y attri butabl e to the rel ati vel y smal l er
formal number of val ence el ectrons i n S3-4compared
to H3-4 (see di scussi on for structure H7).
I n order for the l i berati on of 1-hexene to proceed from
the seven-membered metal l acycl es, H4and S4, reduc-
ti ve -hydrogen mi grati on from C2 to C6 (or from C5 to
Figure 4. DMol
3
/GGA/PW91/DNP opti mi zed stati onary poi nts for
5
-pyrrol e Cl model s.
C1) needs to take pl ace. I nspecti on of the carbon
backbone geometri es i n H4 and S4 reveal s, however,
that none of the -hydrogens are i deal l y posi ti oned to
afford faci l e -hydrogen mi grati on. Sequenti al confor-
mati onal changes from H4 and S4, i nvol vi ng fi rst an
al terati on at C5 (vi a transi ti on structures H4-5 and
S4-5 to yi el d H5 and S5, respecti vel y) and second an
al terati on at C3 (vi a transi ti on structures H5-6 and
S5-6 to yi el d H6 and S6, respecti vel y), afford seven-
membered metal l acycl e geometri es resembl i ng boat
conformati ons i n whi ch both C2 and C5 contai n axi al
-hydrogens sui tabl e for -hydrogen mi grati on. I n thi s
mechani sti c study mi grati on of the axi al -hydrogen on
C2 to C6 of H6and S-6was consi dered for al l model s.
Mi grati on of the axi al -hydrogen of C2 i n H6to C6
l eads to the formati on of an agosti c i ntermedi ate
structure H7 vi a the transi ti on structure H6-7. I n
H6-7 the C2-H di stance el ongates to 1.151 , whi l e
the correspondi ng Cr-H, C1-C2, and H-C6 di stances
decrease to 1.916, 1.499, and 2.347 , respecti vel y. The
C2-H, Cr-H, C1-C2, and H-C6 di stances rel ax to
1.186, 1.750, 1.472, and 2.011 , respecti vel y, i n the
-agosti c i ntermedi ate H7. Al l attempts to opti mi ze an
agosti c i ntermedi ate si mi l ar to H7 for the -bonded
pyrrol e model was unsuccessful ; each attempt resul ted
i n the spontaneous formati on of S6. Thi s resul t i s i n
contrast to the agosti c i nteracti on that was observed for
-pyrrol e i n S3-4, but not for H3-4. Cr-medi ated
hydrogen mi grati on from C2 i n H7 to C6, vi a the
transi ti on structure H7-8, yi el ds 1-hexene coordi nated
to the resul ti ng Cr(I I ) center (H8) vi a -bondi ng i nter-
acti on at the doubl e bond and a remai ni ng agosti c
i nteracti on wi th the mi grated hydrogen. Si mi l ar agosti c-
assi sted hydrogen mi grati on transi ti on structures for
ethyl ene tri meri zati on wi th Ta and Ti catal ysts were
recentl y cal cul ated and reported.
11,12
I n H7-8the Cr-H
(1.637 ), C2-H (1.360), and C6-H (1.549 ) di stances
suggest that the transi ti on state i s rather earl y and i s
more reactant (H7) l i ke. Thi s i s i n contrast to the Cr-
medi ated hydrogen mi grati on transi ti on structure op-
ti mi zed for the -bonded pyrrol e model (S7-8) i n whi ch
the Cr-H (1.627 ), C2-H (1.482 ), and C6-H (1.463
) di stances suggest a l ater transi ti on state than H7-
8, whi ch resembl es the product (S8) more cl osel y than
Figure 5. DMol
3
/GGA/PW91/DNP opti mi zed stati onary poi nts for -pyrrol e Cl model s.
the reagent (S6). A si gni fi cant decrease i n Cr-Py
di stance upon fol l owi ng the sequence H6 f H6-7 f
H7f H7-8f H8of 1.981 f 1.960 f 1.914 f
1.909 f 1.902 i s found, effecti vel y suggesti ng that
contracti on of the
5
-bonded pyrrol e ri ng favors -hy-
drogen mi grati on. A si mi l ar decrease i n Cr-N di stance
for S6f S7-8f S8i s not found, whi ch may rel ate to
the si gni fi cant di fferences found i n acti vati on energi es
for -hydrogen mi grati on for - and
5
-bonded pyrrol e
(vi de i nfra).
Expansi on of the Cl model s to contai n an ani oni c
fragment consi sti ng of tri methyl al umi num chl ori de
(Cl Al Me
3
) was consi dered for al l geometri es i n the
ethyl ene tri meri zati on mechani sti c sequence. A sel ec-
ti on of opti mi zed geometri es for these expanded model s
i s i l l ustrated i n Fi gures 6 and 7 for
5
- and -bonded
pyrrol e, respecti vel y. Compari son of the opti mi zed Cl
model structure H1 wi th the correspondi ng Cl Al Me
3
model structure H1 shows el ongati on of the Cr-Cl
di stance by 0.064 and a Cl -Al coordi nati on di stance
of 2.530 . The el ongati on of the Cr-Cl di stance upon
expansi on of Cl to Cl Al Me
3
i s a general trend observed
for al l opti mi zed geometri es for both bondi ng modes of
pyrrol e. A sl i ght decrease i n coordi nati on di stances of
the pyrrol e l i gand and two ethyl ene fragments i s found
between H1 and H1, whi ch once agai n fol l ows a
consi stent trend for Cr-l i gand di stances for al l geom-
etri es consi dered i n the mechani sti c cycl e. For most
transi ti on structures no si gni fi cant geometri cal di ffer-
ences are observed between the Cl and Cl Al Me
3
model s.
However, a si gni fi cantl y l ess pronounced agosti c i nter-
acti on between Cr-H (2.388 ) i s observed for S3-4
compared to S3-4(2.012 ), whi ch al l ows for a l onger
Cr-C3 (2.259 ) and shorter Cr-C1 (2.113 ) di stance
i n S3-4 compared to Cr-C3 (2.181 ) and Cr-C1
(2.228 ) i n S3-4. The more favorabl e nature of the
S3-4 geometry compared to S3-4 i s refl ected i n the
rel ati vel y l ower acti vati on energy observed i n thi s step
for the Cl Al Me
3
model compared to the Cl model for
-pyrrol e (vi de i nfra). Si mi l arl y, the rel ati vel y shorter
C2-H di stance (1.108 ) and l onger Cr-H di stance
(2.647 ) i n the transi ti on structure H6-7 compared
to the correspondi ng di stances i n H6-7(1.151 and 1.916
, respecti vel y) suggest that the former transi ti on state
(Cl Al Me
3
model ) i s si gni fi cantl y earl i er compared to the
correspondi ng transi ti on state for the Cl model . Nev-
erthel ess, most geometri cal di fferences found for
5
- and
-bonded pyrrol e i n the Cl model s are effecti vel y repro-
duced for the di fferent bondi ng modes of pyrrol e i n the
more real i sti c Cl Al Me
3
model s.
Electronic versusGibbsFreeEnergies. The Cr(I I )
structures H1, S1, H1, and S1 have been chosen as
reference structures to whi ch the energi es of al l stati on-
ary poi nts i n the mechani sti c sequence are rel ated and
corrected wi th the rel evant number of ethyl ene mol -
ecul es. The DMol
3
/GGA/PW91 potenti al energy surfaces
(PESs) for the two Cl model s and two Cl Al Me
3
model s,
i .e., for
5
- and -bonded pyrrol e i n each case, are
i l l ustrated as four separate energy l evel di agrams i n
Fi gure 8. I n each case the rel ati ve el ectroni c energy
di fferences (wi thout the i ncl usi on of zero-poi nt energy
correcti ons and desi gnated as E) and rel ati ve vari a-
ti ons i n cal cul ated Gi bbs free energy correcti ons to the
el ectroni c energi es (wi th the i ncl usi on of ZPE correc-
ti ons), for al l stati onary poi nts i n the proposed mecha-
ni sm, are i l l ustrated. Two temperatures for the Gi bbs
free energy correcti ons, vi z., 298.15 and 375.00 K, are
consi dered for each graph and are desi gnated by G
298
and G
375
, respecti vel y.
A compari son of the el ectroni c (E) and Gi bbs free
energy (G
298
and G
375
) di fferences for
5
-bonded
pyrrole in the Cl model (graph a i n Fi gure 8) shows
essenti al l y no di fferences for the metal l acycl e formati on
sequence H1f H1-2f H2, for whi ch si mi l ar acti va-
ti on (E
a
) 9.7, G
q
298
) 10.4, and G
q
375
) 10.7 kcal /
mol , respecti vel y) and reacti on energi es (E )2.0, G
298
) 1.9, and G
375
) 2.2 kcal /mol , respecti vel y) are found.
I n contrast, however, the metal l acycl e growth sequence
H2fH3-4fH4shows si gni fi cant di fferences for both
cal cul ated acti vati on (E
a
) 13.4, G
q
298
) 29.1, and
G
q
375
) 32.9 kcal /mol , respecti vel y) and reacti on ener-
gi es (E ) -20.9, G
298
) -5.6, and G
375
) -2.4 kcal /
mol , respecti vel y) between the rel ati ve el ectroni c and
Gi bbs free energy val ues. The rel ati vel y l ess favorabl e
reacti on and acti vati on Gi bbs free energi es are attri but-
abl e to unfavorabl e entropy (TS) correcti ons to the
total el ectroni c energi es when an addi ti onal ethyl ene
mol ecul e i s i ntroduced to the mechani sm and i nserted
i nto the fi ve-membered metal l acycl e structure H2(vi de
Figure 6. DMol
3
/GGA/PW91/DNP opti mi zed stati onary
poi nts for
5
-pyrrol e Cl Al Me
3
model s.
i nfra). An essenti al l y constant di fference between cal -
cul ated total el ectroni c energi es (E) and Gi bbs free
energi es (G
298
and G
375
) of ca. 15 and 18 kcal /mol ,
for G
298
and G
375
, respecti vel y, i s found to be mai n-
tai ned for the rest of the mechani sti c sequence H4
through H8.
Figure 7. DMol
3
/GGA/PW91/DNP opti mi zed stati onary poi nts for -pyrrol e Cl Al Me
3
model s.
Figure8. Comparati ve E, G
298
, and G
375
DMol
3
/GGA/PW91/DNP potenti al energy surfaces for
5
- and -pyrrol e for
both the stri pped-down Cl and ful l Cl Al Me
3
ani on model s.
Cal cul ated reacti on and acti vati on el ectroni c energi es
(E), as wel l as the correspondi ng enthal py (H),
entropy (TS), and Gi bbs free energy (G) correcti ons
at 298.15 K, for metal l acycl e formati on and metal l acycl e
growth (for both the Cl and Cl Al Me
3
model s and both
bondi ng modes of pyrrol e) are summari zed i n Tabl e 2.
From Tabl e 2 i t i s evi dent that the TS
298
contri buti ons
to the cal cul ated Gi bbs free energi es for metal l acycl e
formati on i s negl i gi bl e (-1.1 to 0.5 kcal /mol ), whi ch
rel ates to the si mi l ar metal l acycl e formati on H
298
and
G
298
val ues accordi ng to the rel ati on G ) H - TS.
I n contrast, however, rel ati vel y l arge negati ve TS
298
contri buti ons (-14.1 to -12.4 kcal /mol ) to G
298
for
metal l acycl e growth are found. A si mi l ar trend i s
observed for the rel ati ve cal cul ated acti vati on energy
parameters i n whi ch the TS
q
298
contri buti ons to G
q
298
are negl i gi bl e for metal l acycl e formati on (-2.0 to -0.4
kcal /mol ), but si gni fi cantl y negati ve for metal l acycl e
growth (-14.5 to -13.6 kcal /mol ). These unfavorabl e
entropy contri buti ons ari se from the i ncorporati on of an
additional ethylene molecule during metallacycle growth,
essenti al l y converti ng a bi mol ecul ar system to a uni -
mol ecul ar system. The effecti ve Gi bbs free energi es of
acti vati on (G
q
298
) for metal l acycl e growth, i n, for
exampl e, the Cl Al Me
3
sequence H2 f H3-4, show
that consi derati on of onl y el ectroni c energy di fferences
woul d l ead to a 15.8 kcal /mol underesti mati on of the
acti vati on energy determi ned for G
q
298
and serves to
emphasi ze the i mportance of i ncl usi on of free energy
correcti ons to the cal cul ated energy di fferences. A
si mi l ar i ncrease i n the esti mati on of the effecti ve
metal l acycl e growth acti vati on energy by 11.3 kcal /mol ,
upon i ncl usi on of thermodynami c correcti ons at 298.15
K, i s refl ected i n the recentl y reported DFT study on
Ti -catal yzed ethyl ene tri meri zati on by de Brui n et al.
11b
A general compari son of the graphs i n Fi gure 8 shows
that an i ncrease of temperature from 298.15 to 375 K
has no si gni fi cant effect on cal cul ated Gi bbs free energy
di fferences for metal l acycl e formati on. Metal l acycl e
growth i s, however, cal cul ated to proceed wi th a sl i ghtl y
hi gher acti vati on energy for al l four mechani sms rep-
resented i n Fi gure 8. Thi s i ncrease i n G
q
375
compared
to G
q
298
resul ts from an i ncrease i n the negati ve
entropy contri buti on (TS
q
375
) to G
q
375
rel ati ve to the
TS
q
298
contri buti on to G
q
298
(not i ncl uded i n Tabl e
2).
The rel ati vel y constant G correcti on rati os obtai ned
for the di fferent model s are evi dent from the si mi l ar
graphs i n Fi gure 8. Consequentl y, the Gi bbs free energy
di fferences at 298.15 K (G
298
) wi l l be used for al l
energy and mechani sti c compari sons among stati onary
poi nts i n the remai nder of thi s paper. The rel ati ve
energi es for
5
- and -bonded pyrrol e wi l l be compared
for the Cl model, fol l owed by a bri ef di scussi on on the
di fferences obtai ned wi th expansi on to the ClAlMe
3
model. Comparati ve PESs (G
298
) for
5
- and -bonded
pyrrol e are i l l ustrated i n Fi gures 9 and 10 for the Cl
and Cl Al Me
3
model s, respecti vel y. Note that i n each
case the energi es of al l stati onary poi nts are referenced
to the respecti ve cal cul ated G
298
val ues for H1(Fi gure
4) and H1 (Fi gure 6).
5
- versus -Bonded Pyrrole: MetallacycleFor-
mation. Metal l acycl e formati on for
5
-bonded pyrrol e
from H1to H2(Fi gure 4) i s cal cul ated to be endothermi c
Table 2. Reaction (E, H
298
, TS
298
, and G
298
) and Activation (E
a
, H
q
298
, TS
q
298
, and G
q
298
)
Parameters (kcal/mol) for Metallacycle Formation and Metallacycle Growth for Both the Cl and
ClAlMe
3
Models
reacti on step E Ea H H
q
TS TS
q
G G
q
H1f H1-2f H2 2.0 9.7 0.8 9.3 -1.1 -1.1 1.9 10.4
S1f S1-2f S2 -9.3 9.6 -9.1 9.7 -0.7 -1.6 -8.4 11.3
H1 f H1-2 f H2 5.5 9.1 4.6 9.1 0.5 -0.4 4.0 9.5
S1 f S1-2 f S2 -8.0 9.5 -7.4 9.4 -1.2 -2.0 -6.2 11.4
H2f H3-4f H4 -21.0 13.4 -17.9 14.6 -12.4 -14.5 -5.6 29.1
S2f S3-4f S4 -24.7 18.7 -22.2 19.2 -13.2 -14.0 -9.1 33.2
H2 f H3-4 f H4 -23.1 9.2 -20.4 11.1 -14.1 -13.9 -6.3 25.0
S2 f S3-4 f S4 -25.7 7.3 -22.6 8.3 -12.8 -13.6 -9.8 21.8
Figure 9. Rel ati ve G
298
DMol
3
/GGA/PW91/DNP poten-
ti al energy surfaces for
5
- and -pyrrol e for the Cl ani on
model s (kcal /mol ). Al l energi es are rel ati ve to H1corrected
wi th the rel evant number of ethyl ene mol ecul es. Energy
di fferences between two stati onary poi nts are i ndi cated i n
i tal i cs.
Figure10. Rel ati ve G
298
DMol
3
5
- and -pyrrol e for the Cl Al Me
3
ani on model s (kcal /mol ). Al l energi es are rel ati ve to H1
corrected wi th the rel evant number of ethyl ene mol ecul es.
Energy di fferences between two stati onary poi nts are
i ndi cated i n i tal i cs.
by 1.9 kcal /mol and requi res a modest acti vati on barri er,
vi a transi ti on structure H1-2(Fi gure 4), of 10.4 kcal /
mol (Fi gure 9). The preferred conformati on of the fi ve-
membered ri ng of H2i s di ctated by the rel ati ve ori en-
tati on of the ethyl ene fragments i n H1 and H1-2.
Al ternati ve conformati ons for H1, H1-2, and H2were
al so opti mi zed and are i l l ustrated as H1-alt, H1-2-
alt, and H2-alt i n Fi gure 11. The cal cul ated changes
i n G
298
for H1fH2and H1fH1-2-alt are 1.8 and
10.9 kcal /mol , respecti vel y, whi ch i s essenti al l y si mi l ar
to the energi es cal cul ated for H1fH2and H1fH1-
2. I t was consequentl y deci ded to onl y consi der the
conformati on as represented for H2as acti ve i ntermedi -
ate i n the mechani sti c cycl e. The metal l acycl e precursor
for -bonded pyrrol e, S1 (Fi gure 5), i s 1.2 kcal /mol
hi gher (Fi gure 9) i n energy compared to H1, whi ch
suggests that the
5
-bonded mode of pyrrol e wi l l ther-
modynami cal l y be favored at the start of the mecha-
ni sm. The comparati ve acti vati on energy for metal l a-
cycl e formati on for -bonded pyrrol e i s sl i ghtl y hi gher
(11.3 kcal /mol ) compared to
5
-bonded pyrrol e (10.4 kcal /
mol ), whi ch i s i n contrast to the si gni fi cantl y more
favorabl e reacti on energy for S1 f S2 (-8.4 kcal /mol )
compared to H1fH2(1.9 kcal /mol ). Consequentl y, S2
i s 9.1 kcal /mol l ower i n energy than H2, whi ch suggests
that the -bonded mode of pyrrol e wi l l thermodynami -
cal l y be favored for the fi ve-membered metal l acycl e.
Formati on of the fi ve-membered metal l acycl e i nvol ves
an oxi dati ve addi ti on process i n whi ch the oxi dati on
state of Cr formal l y changes from I I to I V.
5
-versus-BondedPyrrole: MetallacycleGrowth.
At thi s stage of the mechani sm a competi ti on between
metal l acycl opentane (H2and S2) decomposi ti on, to yi el d
1-butene, and metal l acycl e growth upon i ncorporati on
of an addi ti onal ethyl ene mol ecul e may be envi saged.
However, 1-butene formati on from metal l acycl open-
tanes was found to be di sfavored compared to metal l a-
cycl e growth i n theoreti cal studi es for Ti -
11
and Ta-
catal yzed
12
ethyl ene tri meri zati on. I n these studi es i t
was found that 1-butene l i berati on from the metal l a-
cycl opentanes proceeds i n a two-step mechani sm whi ch
requi res hi gher acti vati on and reacti on energi es com-
pared to metal l acycl e growth. These rel ati vel y unfavor-
abl e energi es are attri buted to the ri ng strai n of the
metal l acycl opentanes. Therefore, reacti on steps for com-
peti ng 1-butene l i berati on from ei ther H2and S2were
not consi dered i n thi s study.
I n order for metal l acycl e growth to occur from H2an
addi ti onal ethyl ene mol ecul e needs to i nteract wi th Cr.
Ethyl ene coordi nati on to Cr i n H2l eads to the formati on
of the weak -compl ex H3 and i s found to be si gni fi -
cantl y endothermi c by 21.4 kcal /mol (Fi gure 9). Thi s
rel ati vel y hi gh endothermi ci ty i s attri butabl e to two
factors, vi z., an unfavorabl e entropy contri buti on to the
Gi bbs free energy for thi s step i n the mechani sm and
the unprecedented nature of seven-coordi nated Cr com-
pl exes menti oned to earl i er (vi de supra). Consequentl y,
H3i s regarded as a shal l ow l ocal mi ni mum on the path
of effecti ve concerted ethyl ene i nserti on i n the Cr-C1
bond of H2. Al l efforts to opti mi ze a -pyrrol e compl ex
si mi l ar to H3resul ted i n the spontaneous di ssoci ati on
of the ethyl ene fragment from the compl ex, essenti al l y
suggesti ng that i ncorporati on of ethyl ene i n S2wi l l be
l ess favorabl e compared to i ncorporati on of ethyl ene i n
H2. Once agai n, the coordi nati on mode of the pyrrol e
l i gand seems to di ctate thi s di screpancy.
The rel ati vel y l onger Cr-C2 di stance (2.586 ),
compared to Cr-C1 (2.464 ) i n H3, as wel l as the
rel ati vel y l onger Cr-C3 (2.177 ) versus Cr-C6 (2.137
) di stance, suggest coordi nati on of C2 wi th C3 duri ng
metal l acycl e growth. A transi ti on structure (H3-4) for
C2-C3 coordi nati on i n H3connects H3and H4wi th a
barri er of 7.7 kcal /mol and an exothermi ci ty of 27.0 kcal /
mol . Al ternati ve coordi nati on of C1 and C3 i n H3was
al so consi dered and l eads to the formati on of the
transi ti on structure H3-4-alt and seven-membered
metal l acycl e product H4-alt i l l ustrated i n Fi gure 12.
The i ncrease i n energy for H3f H3-4-alt, however,
i s 6.9 kcal /mol hi gher compared to H3fH3-4, maki ng
thi s mode of ethyl ene i nserti on l ess probabl e. The
effecti ve gai n i n energy for metal l acycl e growth H2 +
ethyl ene f H4i s 5.6 kcal /mol wi th an effecti ve acti va-
ti on barri er (H2+ ethyl ene f H3-4) of 29.1 kcal /mol ,
essenti al l y representi ng the rate-determi ni ng step i n the
5
-pyrrol e mechani sm (Fi gure 9). Thi s esti mated barri er
Figure11. DMol
3
/GGA/PW91/DNP opti mi zed structures
of H1-alt, H1-2-alt, and H2-alt. Figure12. DMol
3
of H3-4-alt and H4-alt.
i s sl i ghtl y hi gher than the barri er reported (23.3 kcal /
mol ) for the si mi l ar effecti ve transformati on i n the
cal cul ated Ti -catal yzed tri meri zati on of ethyl ene.
11b
The sequence S1 f S3-4 f S4 proceeds wi th an
acti vati on barri er of 33.1 kcal /mol , for concerted i nser-
ti on of ethyl ene i nto the Cr-C1 bond of S2(Fi gure 5),
and i s exothermi c by 9.1 kcal /mol . Thi s metal l acycl e
growth acti vati on barri er represents the rate-determi n-
i ng step for the -pyrrol e mechani sm. A di rect compari -
son of the rel ati ve energi es for H3-4and S3-4(Fi gure
9) shows that S3-4 i s l ower i n energy than H3-4 by
5.1 kcal /mol . Thi s effecti vel y suggests that the -coor-
di nated pyrrol e geometry wi l l preferenti al l y popul ate
the transi ti on state for metal l acycl e growth i n the
proposed mechani sm. I t i s i nteresti ng to note that an
agosti c i nteracti on between Cr and a hydrogen on C3
i s present i n S3-4, accompani ed by a rel ati vel y short
Cr-C3 di stance, not found for H3-4. A -bonded mode
of pyrrol e i s al so preferred for the seven-membered
metal l acycl e product, S4, whi ch i s found to be 12.6 kcal /
mol l ower i n energy compared to H4.
5
- versus -Bonded Pyrrole: 1-Hexene Libera-
tion. 1-Hexene l i berati on from the di rect metal l acycl e
growth products, H4and S4(Fi gures 4 and 5), coul d i n
pri nci pl e proceed by reducti ve -hydrogen mi grati on
from C2 to C6 (or si mi l arl y from C5 to C1). None of the
-hydrogens i n H4and S4do, however, have a preferred
axi al ori entati on necessary to ensure faci l e -hydrogen
mi grati on. Consequentl y, the potenti al energy surfaces
of these seven-membered metal l acycl e i ntermedi ates
were i nvesti gated i n more detai l by consi deri ng ad-
di ti onal conformati ons of the seven-membered ri ng.
Downward rotati on of C5 i n H4(and S4) vi a transi ti on
structure H4-5 (and S4-5) l eads to the formati on of
the metal l acycl e i ntermedi ate H5(and S5), i n whi ch one
of the -hydrogens on C5 i s posi ti oned i n a formal axi al
ori entati on. The acti vati on energi es for the conforma-
ti onal changes H4f H5and S4f S5are 6.8 and 5.8
kcal /mol , respecti vel y, wi th reacti on energi es -0.7 and
1.3 kcal /mol , respecti vel y. A second subsequent confor-
mati onal change consi dered i nvol ves the downward
rotati on of C3 i n H5(and S5), vi a transi ti on structure
H5-6(and S5-6), to yi el d the semi -chai r geometry H6
(and S6). The acti vati on energi es for thi s second con-
formati onal change are 9.6 and 5.6 kcal /mol for the
respecti ve
5
- and -bonded modes of pyrrol e, wi th
respecti ve reacti on energi es of -0.4 and -1.8 kcal /mol .
After thi s second conformati onal change a -hydrogen
on C-2 i n H6(and S6) i s formal l y axi al , representi ng a
conformati on sui tabl e for -hydrogen mi grati on from C2.
The semi -chai r conformati ons for the seven-membered
ri ngs i n H6 and S6 are di sti ngui shed from the other
conformati ons (H4, H5, S4, and S5) by the sequenti al
trans ori entati ons of axi al hydrogens upon fol l owi ng the
sequence C1 to C6 and are anal ogous to the l owest
energy chai r conformati on for cycl ohexane. Si mi l ar
semi -chai r conformati ons for seven-membered metal l a-
cycl e structures were al so expl i ci tl y consi dered i n
cal cul ated ethyl ene tri meri zati on mechani sms catal yzed
by Ti
11
and Ta.
12
The rel ati vel y l ower energi es obtai ned
for al l -bonded pyrrol e seven-membered metal l acycl es,
as wel l as rel ati vel y l ower acti vati on energi es for
conformati onal changes, compared to the
5
-modes,
suggest that the -bondi ng mode of pyrrol e wi l l be
preferred i n thi s regi on of the potenti al energy surface.
Al though -hydrogen mi grati on may proceed from
ei ther C2 or C5 to C6 and C1 (i n H6 and S6), respec-
ti vel y, onl y the mi grati on from C2 to C6 was consi dered
i n thi s mechani sti c study. Si gni fi cant energy di fferences
are not envi saged for al ternati ve -hydrogen mi grati on
from C5 to C1. -Hydrogen mi grati on i n H6 l eads to
the formati on of an agosti c stabi l i zed i ntermedi ate, H7,
vi a the transi ti on structure H6-7, wi th a l ow barri er
of 4.6 kcal /mol and a reacti on energy of 0.7 kcal /mol .
Subsequent conti nuati on of Cr-medi ated -hydrogen
mi grati on from H7proceeds vi a the transi ti on structure
H7-8, whi ch i s cal cul ated to be 0.5 kcal /mol l ower i n
energy than H7.
32
-hydrogen mi grati on i nvol ves reduc-
ti ve el i mi nati on of the Cr(I V) H6 speci es to the corre-
spondi ng Cr(I I ) speci es, H8, i n whi ch the l i berated
1-hexene fragment i s coordi nated to Cr vi a a -i nterac-
ti on at the doubl e bond and an agosti c i nteracti on wi th
the mi grated hydrogen of C6. To ascertai n whether the
formati on of the agosti c i ntermedi ate geometry, H7, i s
a prerequi si te for the transformati on H6 f H8, an
i ntri nsi c reacti on path (I RP) cal cul ati on i nvol vi ng H6
(reactant), H7-8(transi ti on structure), and H8(prod-
uct) was performed. From the PES mapped by the I RP
cal cul ati on i t was found that H7-8i s di rectl y connected
to the product H8. I n contrast, however, an addi ti onal
equi l i bri um geometry between H6 and H7-8 was
i denti fi ed that corresponded to H7. Thi s resul t empha-
si zed that a stepwi se pathway H6fH7fH8operates
for
5
-pyrrol e i n thi s regi on of the PES, i n contrast to
the resul ts obtai ned for -pyrrol e (vi de i nfra). The
energy gai n for the transformati on H7 f H8 i s 16.8
kcal /mol , whi l e the gai n i n energy for the sequence H6
f H8 i s 16.1 kcal /mol .
Si mi l ar Cr-medi ated -hydrogen mi grati on i n S6was
cal cul ated to proceed i n a concerted fashi on vi a the
transi ti on structure S7-8to the 1-hexene compl ex S8.
No agosti c stabi l i zed i ntermedi ate for the -bonded
pyrrol e model , si mi l ar to H7, was successful l y opti -
mi zed, whi ch i s i n contrast to the agosti c i nteracti on
found for S3-4, but not for H3-4. I RP cal cul ati ons for
S6 (reactant), S7-8 (transi ti on structure), and S8
(product) confi rmed that S7-8i s di rectl y connected to
both S6 and S8. Another i nteresti ng observati on from
thi s I RP cal cul ati on was that rotati on of the pyrrol yl
fragment i n S7-8 rel ati ve to the pyrrol yl ori entati on
i n S6 and S8 takes pl ace spontaneousl y (Fi gure 9).
Several efforts to opti mi ze a transi ti on state geometry
that resembl es the pyrrol yl ori entati on i n S6 and S8
were unsuccessful ; i n each i nstance the transi ti on state
search converged to the S7-8 geometry. The energy
barri er for the transformati on S6fS8i s 14.5 kcal /mol ,
whi ch i s si gni fi cantl y hi gher than the effecti ve barri er
for H6 f H8 (4.6 kcal /mol ). I n addi ti on S6 f S8 i s
endothermi c by 0.9 kcal /mol , whi ch i s i n sharp contrast
to the exothermi c transformati on of H6 f H8 by 16.1
kcal /mol . The rel ati vel y l ower energy of H8 compared
to S8(by 5.0 kcal /mol ) represents one of the few areas
(32) The l ower G298 energy of H7-8compared to H7i s expl ai ned
by the rel ati ve thermodynami c correcti ons to the el ectroni c energi es
of the respecti ve speci es. Consi derati on of purel y el ectroni c energi es
shows that the energy of H7-8 i s 1.5 kcal /mol hi gher i n energy
compared to H7. The total correcti on to the el ectroni c energy at 298.15
K for H7-8i s 15.1 kcal /mol , whereas the correspondi ng correcti on for
H7 i s 17.1 kcal /mol .
on the potenti al energy surface where a
5
-bonded
pyrrol e i ntermedi ate i s more stabl e than the corre-
spondi ng -mode. I n general thi s suggests that the
Cr(I I ) i ntermedi ates prefer a
5
-bondi ng mode of pyrrol e,
whereas the Cr(I V) i ntermedi ates prefer the al ternati ve
-bondi ng mode of pyrrol e.
A si gni fi cant feature of the transi ti on structures
H7-8 and S7-8 i s the parti al coordi nati on of the
mi grati ng hydrogen to the Cr center, effecti vel y empha-
si zi ng a mi grati on process whi ch i s Cr-medi ated. Si mi l ar
agosti c assi sted hydrogen mi grati on mechani sms were
reported by Yu et al .,
12
Bl ok et al .,
11a
and de Brui n et
al .
11b
for 1-hexene l i berati on i n Ta- and Ti -catal yzed
ethyl ene tri meri zati on.
The sel ecti vi ty toward 1-hexene i n the ethyl ene tri -
meri zati on mechani sm i s regul ated by the rel ati ve
acti vati on energi es for competi ng -hydrogen mi grati on
i n H6 and S6 compared to coordi nati on and i nserti on
of an addi ti onal (fourth) ethyl ene mol ecul e i n H6 and
S6. From theoreti cal studi es on Ti
11
and Ta
12
i t was
found that ethyl ene coordi nati on and i nserti on i n re-
specti ve metal l acycl oheptane i ntermedi ates are unfa-
vorabl e compared to metal l acycl oheptane decomposi ti on
to yi el d 1-hexene. Ethyl ene coordi nati on and i nserti on
i n metal l acycl opentane i netermedi ates (H2 and S2) i s
found to be parti cul arl y unfavorabl e i n the current
study. I n addi ti on, the rel ati ve acti vati on energi es for
-hydrogen mi grati on i n H6 and S6 are favorabl e.
Consequentl y, a mechani sm i nvol vi ng further metal l a-
cycl e growth, to yi el d metal l acycl ononane i ntermedi ates
and 1-octene l i berati on, i s not envi saged to be energeti -
cal l y favorabl e and was not consi dered i n the current
study.
General i nspecti on of the potenti al energy surface
depi cted i n Fi gure 9 shows the overal l ethyl ene tri mer-
i zati on transformati ons, H1 + ethyl ene f H8 and S1
+ ethyl ene f S8, are exothermi c by -20.9 and -17.0
kcal /mol , respecti vel y. Thi s i s i n agreement wi th the fact
that Cr-catal yzed tri meri zati on i s a faci l e process. The
rate-determi ni ng step i n the mechani sm i s predi cted to
be metal l acycl e growth wi th G
q
overal l
) 38.2 and 33.1
kcal /mol for
5
- and -bonded pyrrol e, respecti vel y.
These G
q
overal l
val ues are both rel ated to the -pyrrol e
metal l acycl opentane geometry, S2, i n Fi gure 9. Thi s i s
because the
5
-pyrrol e metal l acycl opentane, H2, whi ch
i s hi gher i n energy than S2by 9.1 kcal /mol , i s i n rapi d
equi l i bri um wi th the reference state S2.
ClAlMe
3
Models. Expansi on of the Cl ani on frag-
ment to a more real i sti c Cl Al Me
3
ani oni c fragment was
deemed necessary to ensure cl oser resembl ance of the
theoreti cal model s to actual reagents used i n experi -
mental studi es. The comparati ve potenti al energy sur-
faces for the proposed ethyl ene tri meri zati on mecha-
ni sm for the
5
-bondi ng mode of pyrrol e i s i l l ustrated
i n Fi gure 13 for both the Cl and Cl Al Me
3
model s.
Excel l ent agreement of cal cul ated acti vati on and reac-
ti on energi es i s evi dent for the two model s. The com-
parati ve potenti al energy surfaces for the -bondi ng
mode of pyrrol e (for both the Cl and Cl Al Me
3
model s)
are i l l ustrated i n Fi gure 14. I n contrast wi th the good
agreement observed for
5
-bonded pyrrol e model s (Fi g-
ure 13), a conspi cuous l ower acti vati on energy for S2
fS3-4 fS4 (21.8 kcal /mol ) compared to S2fS3-4
f S4 (33.1 kcal /mol ) i s evi dent from Fi gure 14. Thi s
di fference i s attri buted to si gni fi cant geometri cal di f-
ferences found for the opti mi zed structures of S3-4
and S3-4, al l uded to earl i er, i n whi ch the Cl Al Me
3
fragment i n S3-4 enforces si gni fi cant rel ati ve el onga-
ti on of the Cr-Cl bond, whi ch i n turn resul ts i n more
favorabl e accommodati on of the i nserti ng ethyl ene
fragment. Thi s si gni fi cant l oweri ng of the acti vati on
energy for metal l acycl e growth, upon expansi on of the
ani on fragment from Cl to Cl Al Me
3
, represents a
fundamental l ower i ng of the bar r i er of the r ate-
determi ni ng step i n the overal l proposed mechani sm.
Thi s coul d i n part poi nt to the posi ti ve effect tri al kyl -
al umi nums have on the Cr-catal yzed ethyl ene tri mer-
i zati on.
Ring Slippage. I n Fi gure 9 the rel ati ve energi es of
al l equi l i bri um and transi ti on state geometri es are
presented, for both
5
- and -bondi ng modes of pyrrol e,
rel ati ve to the energy of the
5
-bonded structure H1.
From thi s representati on a di rect energy compari son
between si mi l ar structures wi th di fferent bondi ng modes
for pyrrol e may be made. As poi nted out earl i er, met-
al l acycl e formati on i s preferred for the H1f H1-2f
H2 sequence due to the l ower rel ati ve energy of H1
versus S1, as wel l as the sl i ghtl y l ower acti vati on energy
necessary for metal l acycl e formati on to proceed from the
former. The si gni fi cantl y l ower energy of S2compared
to H2 suggests, however, that a transformati on from
H2 to S2 wi l l be favored on thermodynami c grounds.
Such a transformati on may be real i zed through a ri ng
sl i ppage mechani sm i n whi ch the bondi ng mode of
pyrrol e formal l y changes from
5
to . The concept of
l i gand ri ng sl i ppage i n organometal l i c chemi stry, espe-
ci al l y wi th reference to
5
T
3
haptotropi c shi fts for
298
DMol
3
5
-pyrrol e Cl and Cl Al Me
3
ani on
model s (kcal /mol ).
298
DMol
3
ti al energy surfaces for -pyrrol e Cl and Cl Al Me
3
ani on
model s (kcal /mol ).
cycl opentadi enyl and i ndenyl l i gands,
33
i s wel l docu-
mented. Experi mental studi es by Kershner and Basol o
34
on
5
-heterocycl i c manganese tri carbonyl compl exes al so
suggest that pyrrol e ri ng sl i ppage i s more faci l e com-
pared to the i soel ectroni c cycl opentadi enyl l i gand. Re-
centl y, theoreti cal studi es by Vei ros
35
on pyrrol yl Mn
compl exes showed that pyrrol e ri ng sl i ppage essenti al l y
occurs between
5
- and -bondi ng modes, wi th no l ocal
mi ni mum found for a
3
-bondi ng mode. Thi s i s i n
contrast to the preferred
5
T
3
bondi ng mode changes
observed for cycl opentadi enyl deri vati ves.
Three areas on the potenti al energy surface di spl ayed
i n Fi gure 9 were i denti fi ed where ri ng sl i ppage of the
pyrrol e l i gand may have an i mpact on the cal cul ated
energeti cs, vi z., the fi ve-membered metal l acycl es (H2
T S2), the seven-membered metal l acycl es (H6 T S6),
and the 1-hexene coordi nati on compl exes (H8 T S8).
The transi ti on structures for ri ng sl i ppage between
these equi l i bri um structures were successful l y opti -
mi zed and are i l l ustrated as R2, R6, and R8i n Fi gure
15 for H2T S2, H6T S6, and H8T S8, respecti vel y.
The coordi nati on of pyrrol e i n R2 resembl es a di s-
torted
3
-bondi ng mode i n whi ch the Cr-C2 (2.448 )
and Cr-C5 (2.256 ) di stances are not si mi l ar
36
and
the Cr-N di stance (2.018 ) i s el ongated compared to
the Cr-N di stance i n S2(1.873 ). As menti oned above,
the metal l acycl e transi ti on structure, H1-2, i s ener-
geti cal l y favored, and i t i s thus assumed that H2 wi l l
be the di rect metal l acycl e product. Transformati on of
H2to S2, vi a the ri ng sl i ppage transi ti on structure R2,
i s cal cul ated to proceed wi th a l ow acti vati on barri er of
2.6 kcal /mol and a gai n i n energy of 9.1 kcal /mol , as
summari zed i n Tabl e 3. Thi s faci l e predi cted change of
bondi ng mode emphasi zes the probabi l i ty that the
-pyrrol e fi ve-membered metal l acycl e i s a thermody-
nami c si nk i n thi s area of the potenti al energy surface.
Metal l acycl e growth necessari l y then i nvol ves S2, and
not H2, as the di rect reagent structure. I nserti on of
ethyl ene i nto the Cr-C1 bond of S2i s cal cul ated to be
a concerted process and proceeds wi th a rather hi gh one-
step acti vati on barri er of 33.1 kcal /mol (Fi gure 9).
Neverthel ess, the l ower rel ati ve energy of the -pyrrol e
metal l acycl e growth transi ti on structure, S3-4, com-
pared to the
5
-pyrrol e counterpart, H3-4, suggests
that the -coordi nati on mode domi nates i n thi s regi on
of the PES and that ri ng sl i ppage pri or or duri ng
metal l acycl e growth i s unl i kel y (Fi gure 9).
The rel ati vel y l ower energi es of S4, S5, and S6, as
wel l as the more favorabl e acti vati on energi es for
conformati onal changes of the seven-membered metal -
l acycl es, compared to the
5
-anal ogues suggest that ri ng
sl i ppage of the pyrrol e ri ng wi l l most l i kel y not be
operati ng i n thi s area of the potenti al energy surface.
The rel ati vel y l ower energy of the -hydrogen mi grati on
transi ti on structure H7-8 compared to S7-8 does,
however, suggest that f
5
ri ng sl i ppage i n the most
l i kel y precursor, S6, i s probabl e. The coordi nati on of
pyrrol e i n the transi ti on structure for S6 T H6 ri ng
sl i ppage, R6(Fi gure 15), i nvol ves a di storted
3
-bondi ng
mode si mi l ar to the geometry of R2. The acti vati on
energy for the sequence S6 f R6 f H6 i s 14.6 kcal /
mol and i s endothermi c by 12.0 kcal /mol (Tabl e 3). Thi s
acti vati on barri er shoul d be compared to the competi ng
mechani sti c sequence S6fS7-8fS8, whi ch proceeds
wi th an al most i denti cal acti vati on energy of 14.5 kcal /
mol (Fi gure 9). Consequentl y, no preference i s found for
ri ng sl i ppage (S6fH6) or -pyrrol e -hydrogen mi gra-
ti on on ki neti c grounds. However, i nspecti on of the
rel ati ve energy profi l es i n Fi gure 9 reveal s that the
-hydrogen mi grati on barri er (for
5
-bonded pyrrol e) i s
di ctated by the acti vati on barri er for formati on of the
agosti c i ntermedi ate H7, from whi ch subsequent 1-hex-
ene l i berati on essenti al l y proceeds wi thout barri er. I t
i s thus envi saged that -hydrogen mi grati on from S6,
wi th concomi tant ri ng sl i ppage, wi l l gi ve preval ence to
a di rect mechani sti c sequence S6f H7, whi ch shoul d
not onl y represent the l owest energy path for -hydro-
gen mi grati on from S6but al so provi de for the formati on
of the thermodynami cal l y more favored 1-hexene com-
pl ex, H8. Thi s reasoni ng i s further supported by the
si gni fi cantl y earl i er nature of the transi ti on state, H7-
8, compared to S7-8 (vi de supra).
The earl i er nature of H7-8, compared to S7-8, i s
rel ated to the rel ati ve Cr-l i gand di stance fl exi bi l i ty i n
the proposed mechani sm. I n Fi gure 16 the rel ati ve Cr-
(33) OConnor, J. M.; Casey, C. P. Chem. Rev. 1987, 87, 307.
(34) Kershner, D. L.; Basol o, F. J . Am. Chem. Soc. 1987, 109, 7396.
(35) Vei ros, L. F. J . Organomet. Chem. 1999, 587, 221.
(36) Thi s di storted
3
-coordi nati on mode of the pyrrol e l i gand i n R2
may al so be descri bed as a di storted
2
-coordi nati on mode i n whi ch N
and one adjacent C i n the pyrrol e ri ng are mostl y i nvol ved i n the
bondi ng. Thi s effect i s more pronounced i n the geometri es of R6and
R8.
Figure15. DMol
3
of R2, R6, and R8.
Table 3. Calculated Activation and Reaction
Gibbs Free Energies (298.15 K) for Selected
Pyrrole Ring Slippage Transformations
ri ng sl i ppage
transformati on
G
q
298
(kcal /mol )
G298
(kcal /mol )
H2f S2 2.6 -9.1
S2f H2 11.7 9.1
H6f S6 2.6 -12.0
S6f H6 14.6 12.0
H6f S6 10.9 5.0
S6f H6 5.9 -5.0
pyrrol e di stances
37
for
5
- and -bonded pyrrol e, for al l
stati onary poi nts (Fi gures 9 and 10), are pl otted agai nst
the reacti on coordi nate. I n general , i t i s found that
whereas the Cr--pyrrol e di stances show a maxi mum
di fference of 0.035 wi th no si gni fi cant trend al ong the
reacti on coordi nate, the Cr-
5
-pyrrol e di stances show
a maxi mum di fference of 0.097 and a defi ni te trend
rel ated to the oxi dati on state of Cr. The Cr(I I ) speci es,
H1 and H8, exhi bi t rel ati vel y short Cr-pyrrol e di s-
tances of 1.902 and 1.927 , whereas the Cr(I V) speci es
have an average Cr-pyrrol e di stance of 1.975 . Upon
fol l owi ng the mechani sti c sequence H6f H6-7f H7
fH7-8fH8, an i ncremental decrease i n Cr-pyrrol e
di stances of 1.981 f 1.960 f 1.914 f 1.909 f 1.902
i s observed (Fi gure 16), effecti vel y suggesti ng that a
cl oser proxi mi ty of the
5
-bonded ri ng wi l l favor the
reducti ve el i mi nati ve -hydrogen mi grati on process. A
si mi l ar Cr-pyrrol e di stance contracti on i s not observed
duri ng -hydrogen mi grati on of the -bonded pyrrol e
compl ex S6to S8. The apparentl y favorabl e contracti on
of the
5
-bonded pyrrol e i n the fi nal stage of the
proposed mechani sm i s al so refl ected i n the rel ati vel y
earl y nature of the transi ti on structure H7-8compared
to S7-8, i n whi ch a rel ati vel y short C2-H di stance of
1.360 for the former i s observed versus 1.482 for
the l atter.
The
5
-pyrrol e 1-hexene coordi nati on compl ex, H8, i s
5.0 kcal /mol l ower i n energy compared to the corre-
spondi ng -pyrrol e compl ex, S8. Therefore, i f the S8
compl ex i s the preferred di rect 1-hexene coordi nati on
compl ex, ri ng sl i ppage from S8to H8i s l i kel y, whi ch i s
cal cul ated to proceed wi th an acti vati on barri er of 5.9
kcal /mol . Transformati on of H1from H8by substi tuti on
of 1-hexene wi th 2 equi v of ethyl ene regenerates the
fi rst acti ve i ntermedi ate i n the proposed ethyl ene tri -
meri zati on cycl e.
Population Analysis. The cal cul ated Hi r shfel d
charges l ocated on Cr, the pyrrol e ri ng,
38
and Cl for al l
stati onary poi nts on the potenti al energy surface of the
Cl model s are graphi cal l y i l l ustrated i n Fi gure 17. The
average charges on Cr and pyrrol e for the
5
-bonded
pyrrol e model s i n Fi gure 17 are 0.445 and -0.039 e,
respecti vel y, whi l e the correspondi ng average charges
on Cr and pyrrol e for the -bonded pyrrol e model s are
0.511 and -0.201 e, respecti vel y. The sl i ghtl y l ess
posi ti ve charge on Cr and si gni fi cantl y l ess negati ve
charge on pyrrol e, for the
5
-bonded model s compared
to the -bonded model s, suggest that the charge di stri -
buti on between metal and l i gand for the former i s more
di spersed compared to the l atter. Thi s effect i s more
pronounced between pyrrol e and Cr for the two model s
than for Cr and Cl , as i s evi dent from the si mi l ar
average Hi rshfel d charges on Cl for the
5
- (-0.234 e)
and -bonded pyrrol e (-0.213 e) model s.
The Hi rshfel d charges on Cr, wi th the excepti on of
H3, H3-4, and S3-4, are rel ated to the formal oxi da-
ti on state of Cr. The Cr(I I ) compl exes at the begi nni ng
and end of the proposed mechani sm exhi bi t rel ati vel y
smal l er posi ti ve charges on Cr compared to the Cr(I V)
compl exes. Thi s i s i n agreement wi th a l ess pronounced
el ectron di stri buti on at the Cr center for the Cr(I V)
oxi dati on state compared to the Cr(I I ) oxi dati on state.
The rel ati ve l oweri ng i n posi ti ve charge on Cr for H3,
H3-4, and S3-4 i s qual i tati vel y attri buted to the
i ntroducti on of addi ti onal el ectron densi ty to the Cr
center upon i ncorporati on of a thi rd ethyl ene fragment
to the catal yti c cycl e. Thi s l oweri ng of charge on Cr i s
consi stent wi th temporary expansi on of coordi nati on
number of Cr for ethyl ene coordi nati on (H3) and con-
certed ethyl ene i nserti on (H3-4 and S3-4). I t i s al so
i nteresti ng to note that a good correl ati on between
charge vari ati on on Cr and di stance between Cr and the
5
-bonded pyrrol e ri ng (see Fi gure 16) exi sts.
(37) The Cr-pyrrol e di stances for
5
-bonded pyrrol e refer to the
di stance of the Cr-pyrrol e centroi d axi s, whereas the Cr-pyrrol e
di stances for -bonded pyrrol e refer to the Cr-N di stances.
(38) The total Hi rshfel d charge of the pyrrol e ri ng i s cal cul ated by
summati on of al l Hi rshfel d charges l ocated on the respecti ve atoms i n
the ri ng.
Figure 16. Vari ati on i n Cr-pyrrol e di stance for
5
- and
-pyrrol e (Cl model ) al ong the reacti on coordi nate of the
proposed mechani sm.
Figure 17. Rel ati ve DMol
3
/GGA/PW91/DNP cal cul ated
Hi rshfel d charges on Cr, pyrrol e, and Cl for
5
- and
-pyrrol e (Cl model ).
Conclusions
I n thi s theoreti cal contri buti on on Cr-catal yzed tri -
meri zati on of ethyl ene a mechani sm i s proposed for the
Phi l l i ps (Cr-pyrrol yl ) tri meri zati on catal yst system and
energi es for the di fferent steps are cal cul ated at the
nonl ocal DFT(DMol
3
/GGA/PW91/DNP) l evel of theory.
A detai l ed anal ysi s to determi ne the preferred ground
spi n state for the acti ve Cr(I I ) and Cr(I V) speci es i n the
mechani sm was conducted. From these cal cul ati ons i t
was determi ned that the tri pl et spi n states for both
Cr(I I ) and Cr(I V) are predi cted to be the ground state
at the GGA/PW91 l evel of theory. Both addi ti onal
possi bl e spi n states for the Cr(I I ) speci es (si ngl et and
qui ntet), as wel l as the si ngl et spi n state for Cr(I V)
speci es, were found to be si gni fi cantl y more unfavorabl e
based on rel ati ve el ectroni c energi es. The mai n concl u-
si on from these resul ts was that spi n state crossi ng
duri ng the proposed mechani sm i s unl i kel y to occur,
effecti vel y el i mi nati ng the necessi ty to l ocate mi ni mum
energy crossi ng poi nts (MECPs) for the proposed mech-
ani sm. The proposed ethyl ene tri meri zati on mechani sm
i s based on the formati on of metal l acycl e i ntermedi ates.
Two i mportant features of the proposed mechani sm
were expl i ci tl y i nvesti gated: fi rst, the preferred coor-
di nati on mode of the pyrrol e l i gand i n each step of the
mechani sm, and second, the i mportance of expansi on
of a model Cl ani on to a more real i sti c Cl Al Me
3
ani on
fragment.
The cal cul ated Gi bbs free energy profi l es at 298.15
K (Cl model ) for the ful l potenti al energy surfaces of
5
- and a -coordi nated pyrrol e were both found to be
favorabl e on thermodynami c grounds, wi th G
overal l
)
-20.9 and -17.1 kcal /mol , respecti vel y. The rate-
determi ni ng step i n the mechani sm for both bondi ng
modes of pyrrol e was metal l acycl e growth from the
correspondi ng metal l acycl opentane reagent to the met-
al l acycl oheptane product wi th G
q
overal l
) 38.2 and 33.1
kcal /mol for
5
- and -bonded pyrrol e, respecti vel y. We
have shown that the change of pyrrol e bondi ng mode i s
an i mportant concept i n the proposed mechani sm. A
5
-
bondi ng mode of pyrrol e i s cal cul ated to be favored for
metal l acycl e formati on, whereas a -bondi ng mode i s
favored for metal l acycl e growth and changes i n confor-
mati ons of seven-membered metal l acycl e i ntermedi ates.
No preference was found for
5
- or -pyrrol e i n the fi nal
reducti ve el i mi nati ve l i berati on of 1-hexene i n the
proposed mechani sm. Transi ti on state geometri es were
cal cul ated for pyrrol e ri ng sl i ppage (
5
T) for sel ected
stati onary poi nts on the potenti al energy surface, whi ch
showed that the acti vati on barri er for bondi ng mode
change i s smal l . These theoreti cal resul ts thus suggest
that faci l e change of pyrrol e bondi ng mode enhances the
catal yti c effi ci ency of the Cr-pyrrol yl ethyl ene tri mer-
i zati on.
Potenti al energy surface cal cul ati ons on the more
real i sti c Cl Al Me
3
ani on model s showed remarkabl e
si mi l ari ti es to the PES obtai ned for the stri pped-down
Cl model s. One i mportant di fference for cal cul ated
acti vati on energy for metal l acycl e growth was, however,
found for the -coordi nated pyrrol e model s. A si gni fi cant
l oweri ng of acti vati on energy of the rate-determi ni ng
step by 11.3 kcal /mol i s found for the Cl Al Me
3
model
compared to the stri pped-down Cl model i n thi s step.
Thi s resul t suggests that the ful l al umi nate ani on may
have an i mportant rol e i n control l i ng the reacti vi ty of
the Cr-pyrrol yl catal yst system.
Acknowledgment. We acknowl edge Mr. I van
Bester (I nformati on Management, Sasol ) for the effi ci ent
way i n whi ch he manages al l techni cal software and
hardware requi rements of the Mol ecul ar Model i ng
department at Sasol Technol ogy. We al so wi sh to thank
the members of the Sasol ethyl ene tri meri zati on group
for frui tful di scussi ons and Sasol Technol ogy Ltd for
permi ssi on to publ i sh thi s work.
Supporting Information Available: Cartesi an coordi -
nates for al l opti mi zed geometri es. Thi s i nformati on i s avai l -
abl e free of charge vi a the I nternet at http://pubs.acs.org.
OM0306269

A DFT Study Toward The Mechanism of

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

A DFT Study Toward The Mechanism of

Încărcat de

Drepturi de autor:

Formate disponibile

Articles

A DFT Study toward the Mechanismof

and Petrus J. Steynberg*

Sasol Technol ogy (Pty) Ltd.

Sasol Technol ogy UK.

Accel rys I nc.

S-ar putea să vă placă și