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PAPER www.rsc.org/dalton | Dalton Transactions

Isomerism in rhodium(I) N,S-donor heteroscorpionates: ring substituent and

ancillary ligand effects†
Robin J. Blagg,‡ Neil G. Connelly,* Mairi F. Haddow, Alex Hamilton, Matteo Lusi, A. Guy Orpen and
Benjamin M. Ridgway
Received 2nd July 2010, Accepted 23rd September 2010
DOI: 10.1039/c0dt00774a

The heteroscorpionate ligands [HB(taz)2 (pzR )]- (pzR = pz, pzMe2 , pzPh ) and [HB(taz)(pz)2 ]- ,
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

synthesised from the appropriate potassium hydrotris(pyrazolyl)borate salt and

4-ethyl-3-methyl-5-thioxo-1,2,4-triazole (Htaz), react with [{Rh(cod)(m-Cl)}2 ] to give [Rh(cod)Tx]
{Tx = HB(taz)2 (pz), HB(taz)2 (pzMe2 ), HB(taz)2 (pzPh ), HB(taz)(pz)2 }; the heteroscorpionate
rhodaboratrane [Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}] is the only isolable product from the reaction of
[{Rh(nbd)(m-Cl)}2 ] with K[HB(taz)2 (pzMe2 )]. Carbonylation of the cod complexes gave a mixture of
[Rh(CO)2 Tx] and [(RhTx)2 (m-CO)3 ] which reacts with PR3 to give [Rh(CO)(PR3 )Tx] (R = Cy, NMe2 ,
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Ph, OPh). In the solid state the complexes are square planar with the particular structure dependent on
the steric and/or electronic properties of the scorpionate and ancillary ligands. The complex
[Rh(cod){HB(taz)(pz)2 }] has the heteroscorpionate k2 [N2 ]-coordinated to rhodium with the B–H bond
directed away from the rhodium square plane while [Rh(cod){HB(taz)2 (pzMe2 )}] is k2 [SN]-coordinated,
with the B–H bond directed towards the metal. The complexes [Rh(CO)(PPh3 ){HB(taz)2 (pz)}] and
[Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}] are also k2 [SN]-coordinated but with the pyrazolyl ring cis to PPh3 ;
in the former the B–H bond is directed towards rhodium while in the latter the ring is pseudo-parallel to
the rhodium square plane, as also found for [Rh(CO)2 {HB(taz)2 (pzMe2 )}]. The analogues
[Rh(CO)(PR3 ){HB(taz)2 (pzMe2 )}] (R = Cy, NMe2 ) have the phosphines trans to the pyrazolyl ring.
Uniquely, [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] is k2 [S2 ]-coordinated. A qualitative mechanism is given for
the rapid ring-exchange, and hence isomerisation, observed in solution.

Introduction The extensive, and recently reviewed,7 chemistry of

In recent years the range of scorpionate ligands available for the
synthesis of novel metal complexes has expanded beyond the
archetypal N-donors, i.e. the hydrotris(pyrazolyl)borates {TpR
or HB(pzR )3 },1 to include S-donors such as hydrotris(2-thio-1-
methyl-imidazolyl)borate {TmMe or HB(mtMe )3 }2 and hydrotris(4-
ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate {Tt or HB(taz)3 }
which acts as either an N- or S-donor depending on the metal
to which it coordinates.3 The majority of these ligands are ho-
moscorpionates, i.e. all the donor groups are equivalent. However,
there are limited reports of heteroscorpionates incorporating both
N-donor pyrazolyl (pzR ) and S-donor thioimidazolyl (mtR ) rings.
These include the SN 2 -donors [HB(mtR )(pz)2 ]- (R = Pri , But )4 and
the S2 N-donors [HB(mtMe )2 (pz)]- ,5 [HB(mtR )2 (pz3-Ph,5-Me )]- (R =
Me, Ph, aryl) and [HB(mtBut )2 (pz3-But,5-Me )]- ,6 the zinc(II) complexes
of which have been explored as models of enzyme active sites.
School of Chemistry, University of Bristol, Bristol, U.K., BS8
1TS. E-mail: neil.connelly@bristol.ac.uk; Fax: +44(0)117 9290509;
Tel: +44(0)117 9288162
† Electronic supplementary information (ESI) available: X-ray structure of
10 and 17; variable temperature 1 H NMR spectra of 21; low temperature
1
H NMR spectroscopic data for 6, 7 and 21. CCDC reference numbers
783349 and 792567–792574. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c0dt00774a
‡ Current address: School of Chemistry, The University of Manch-
ester, Oxford Road, Manchester, M13 9PL, U.K. E-mail: robin.blagg@
manchester.ac.uk
tris(pyrazolyl)borate rhodium scorpionates includes the oxidation
of rhodium(I) TpMe2 complexes to give rhodium(II) species sta-
bilised by coordination of the third pyrazolyl ring (i.e. by redox-
induced isomerisation).8 The rhodium chemistry of the S-donor
Tm, and of Tt (which acts as an S-donor to rhodium), differs
from that of the N-donors, TpR , in that the scorpionate is k2 [S2 ]-
coordinated in [RhLL¢Tx] {LL¢ = diene, (CO)(PR3 ); Tx = Tm,9
Tt10 }. Moreover, reacting rhodium(I) and rhodium(III) precursors
with TmR can lead to B–H bond activation and the formation
of octahedral rhodaboratranes (incorporating a rhodium–boron
bond).11,12 Rhodaboratranes have also been directly synthesised
from the rhodium(I) scorpionate complexes [Rh(CO)(PR3 )Tx]
(Tx = Tm,9 Tt10 ) by two-electron oxidation in the presence of
base.
Because of the very different chemistry of the nitrogen- and
sulfur-donor homoscorpionate complexes of rhodium, we decided
to investigate a range of analogous S2 N- and N 2 S-donors in-
corporating pyrazolyl (pzR ) and thioxotriazolyl (taz) groups and
now show how the ring substituents and ancillary ligands affect
structure in the solid state and solution.
Results and discussion
Synthesis and characterisation of heteroscorpionate ligands
Four new heteroscorpionate ligands, namely the S2 N-donors
[HB(taz)2 (pzR )]- (pzR = pz 1- , pzMe2 2- , pzPh 3- ) and the N 2 S-donor

11616 | Dalton Trans., 2010, 39, 11616–11627 This journal is © The Royal Society of Chemistry 2010
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in the melt and driven by sublimation of the liberated pyrazole

onto the cold upper surface of the vessel. The purity and yield of
the product are highly sensitive to both temperature and reaction
time; optimised conditions were 130, 125, 150 and 100 ◦ C, and 60,
90, 90 and 60 min, for K+ 1- , K+ 2- , K+ 3- and K+ 4- respectively,
giving repeatable yields and composition. In each case the pure salt
was isolated by adding thf or CH2 Cl2 to the crude product and
vigorously agitating the mixture to generate a white suspension
which was isolated by filtration, washed with further solvent
and dried in vacuo. The pure white solids (Table 1) were air-
stable, sparingly soluble in highly polar solvents such as dmso
and methanol, and insoluble in solvents such as acetone, thf and
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

Scheme 1
[HB(taz)(pz)2 ]- 4- (Scheme 1), were synthesised by combining the
potassium salt of the appropriate tris(pyrazolyl)borate ligand, i.e.
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CH2 Cl2 .
The NMR spectra of K+ 1- –K+ 4- (Table 2) were assigned
by comparison with those of KTt and KTpR under the same
conditions. The 1 H spectra showed very broad B–H resonances
with half height widths of between 200 and 250 Hz. The only
ambiguities in the assignment of the spectra are in distin-

Tp, TpMe2 or TpPh , with 4-ethyl-3-methyl-5-thioxo-1,2,4-triazole, guishing between the 3- and 5-positions for the pyrazolyl rings
Htaz, in a sealed reaction vessel under a static vacuum. The vessel and the overlapping pyrazolyl and phenyl 13 C resonances of
was heated to the required temperature, the reaction occurring K+ 3- .

Table 1 Analytical data for potassium heteroscorpionates

Analysis / %a
Compound Colour Yield / % C H N
+ -
K[HB(taz)2 (pz)] K 1 white 38 38.6 (38.8) 4.9 (5.0) 27.5 (27.8)
K[HB(taz)2 (pzMe2 )] K+ 2- white 77 41.7 (41.9) 5.5 (5.6) 25.8 (26.0)
K[HB(taz)2 (pzPh )] K+ 3- white 52 56.5 (56.6) 3.9 (3.9) 19.4 (19.6)
K[HB(taz)(pz)2 ] K+ 4- white 42 40.1 (40.4) 4.4 (4.6) 29.7 (30.0)
a
Calculated values in parentheses.

Table 2 Proton, 13 C-{1 H} and 11 B-{1 H} NMR spectroscopic data for potassium heteroscorpionatesa

1 13
Compound H C-{1 H} 11
B-{1 H}

K[HB(taz)2 (pz)] K+ 1-
K[HB(taz)2 (pzMe2 )] K+ 2-
K[HB(taz)2 (pzPh )] K+ 3-
K[HB(taz)(pz)2 ] K+ 4-
a
Chemical shift (d) in ppm, J values in Hz, spectra in d 6 -dmso at 25 ◦ C.
7.28 (br s, 1H, pz 3/5-H), 7.22 (br s, 1H, pz 168.24 (s, 2C, taz C 5 ), 146.21 (s, 2C, taz C 3 ), –4.05 {br s, HB(taz)2 (pz)}
3/5-H), 5.94 (br s, 1H, pz 4-H), 4.96 (v.br s, 137.66 (s, 2C, C 3,5 ), 102.21 (s, 1C, C 4 ), 37.83 (s,
1H, BH), 3.94 (q, 2H, 3 J HH 7.0, taz 2C, taz 4-CH2 CH3 ), 13.34 (s, 2C, taz 3-CH3 ),
4-CH 2 CH3 ), 3.92 (q, 2H, 3 J HH 7.0, taz 10.80 (s, 2C, taz 4-CH2 CH3 )
4-CH 2 CH3 ), 2.20 (s, 6H, taz 3-CH 3 ), 1.14 (t,
6H, 3 J HH 7.0, taz 4-CH2 CH 3 )
5.48 (s, 1H, pz 4-H), 4.98 (v.br s, 1H, BH), 3.93 168.27 (s, 2C, taz C 5 ), 146.29 (s, 2C, taz C 3 ), –5.93 {br s, HB(taz)2 (pz)}
(q, 2H, 3 J HH 7.0, taz 4-CH 2 CH3 ), 2.24 (s, 6H, 144.60 (s, 1C, C 3/5 ), 142.81 (s, 1C, C 3/5 ), 103.09
4
taz 3-CH 3 ), 2.07 (s, 3H, pz 3/5-CH 3 ), 2.00 (s, (br s, 1C, C ), 37.90 (s, 2C, taz 4-CH2 CH3 ),
3H, pz 3/5-CH 3 ), 1.14 (t, 6H, 3 J HH 7.0, taz 13.67 (s, 1C, pz 3/5-CH3 ), 13.34 (s, 2C, taz
4-CH2 CH 3 ) 3-CH3 ), 12.48 (s, 1C, pz 3/5-CH3 ), 10.84 (s,
2C, taz 4-CH2 CH3 )
7.73 (d, 2H, 3 J HH 7.3, pz 3-Phortho ), 7.31 (dd, 2H, 168.13 (s, 2C, taz C 5 ), 146.10 (s, 2C, taz C 3 ), –4.34 {br s, HB(taz)2 (pz)}
3
J HH 7.3, 3 J HH 7.3, pz 3-Phmeta ), 7.22 (br s, 1H, 135.44 (s, 1C, C 5 ), 128.13 (s, 2C, pz 3-Ph),
pz 5-H), 7.16 (t, 1H, 3 J HH 7.3, pz 3-Phpara ), 6.37 125.79 (s, 1C, pz C 3 / pz 3-Ph), 124.60 (s, 2C,
(d, 1H, 3 J HH 2.0, pz 4-H), 4.92 (v.br s, 1H, BH), pz 3-Ph), 122.33 (s, 1C, pz C 3 / pz 3-Ph),
3.95 (q, 2H, 3 J HH 7.1, taz 4-CH 2 CH3 ), 3.93 (q, 121.96 (s, 1C, pz C 3 / pz 3-Ph), 100.05 (s, 1C,
2H, 3 J HH 7.1, taz 4-CH 2 CH3 ), 2.28 (s, 6H, taz C 4 ), 37.80 (s, 2C, taz 4-CH2 CH3 ), 13.37 (s, 2C,
3-CH 3 ), 1.15 (t, 6H, 3 J HH 7.0, taz 4-CH2 CH 3 ) taz 3-CH3 ), 10.92 (s, 2C, taz 4-CH2 CH3 )
7.41 (m, 2H, pz 3/5-H), 7.28 (m, 2H, pz 168.18 (s, 1C, taz C 5 ), 146.52 (s, 1C, taz C 3 ), –3.87 {s, HB(pz)2 (taz)}
3/5-H), 5.97 (m, 2H, pz 4-H), 4.93 (v.br s, 1H, 137.89 (s, 2C, C 3/5 ), 133.15 (s, 2C, C 3/5 ), 102.36
3 4
BH), 3.94 (q, 2H, J HH 7.1, taz 4-CH 2 CH3 ), (s, 2C, C ), 37.90 (s, 1C, taz 4-CH2 CH3 ), 13.33
2.25 (s, 3H, taz 3-CH 3 ), 1.15 (t, 3H, 3 J HH 7.1, (s, 1C, taz 3-CH3 ), 10.83 (s, 1C, taz 4-CH2 CH3 )
taz 4-CH2 CH 3 )

This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 11616–11627 | 11617
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Synthesis and characterisation of rhodium(I) heteroscorpionate Table 3 IR spectroscopic data for rhodium heteroscorpionate carbonyl
complexes complexes

Reacting K+ 1- –K+ 4- with [{Rh(cod)(m-Cl)}2 ] in CH2 Cl2 gave Complex n(CO)/cm-1

the rhodium(I) cycloocta-1,5-diene complexes [Rh(cod)Tx]
[Rh(CO)2 {HB(taz)2 (pz)}] 9a 2083, 2018
{Tx = HB(taz)2 (pz) 5, HB(taz)2 (pzMe2 ) 6, HB(taz)2 (pzPh ) 7, [Rh(CO)2 {HB(taz)2 (pz)}] 9b 2072, 1996
HB(taz)(pz)2 8} (Scheme 2) which were precipitated as [Rh(CO)2 {HB(taz)2 (pzMe2 )}] 10 2078, 2013
yellow-orange solids following addition of n-hexane. Bub- [Rh(CO)2 {HB(taz)2 (pzPh )}] 11a 2080, 2014
[Rh(CO)2 {HB(taz)2 (pzPh )}] 11b 2074, 2009
bling carbon monoxide through CH2 Cl2 solutions of com- [Rh(CO)2 {HB(taz)(pz)2 }] 12a 2084, 2019
plexes 5–8 led to the observation by IR spectroscopy of [Rh(CO)2 {HB(taz)(pz)2 }] 12b 2071, 1997
the rhodium dicarbonyls [Rh(CO)2 Tx] {Tx = HB(taz)2 (pz) 9, [(Rh{HB(taz)2 (pz)})2 (m-CO)3 ] 13 1833 (br)
HB(taz)2 (pzMe2 ) 10, HB(taz)2 (pzPh ) 11, HB(taz)(pz)2 12} and the [(Rh{HB(taz)2 (pzMe2 )})2 (m-CO)3 ] 14 1831 (br)
[(Rh{HB(taz)(pz)2 })2 (m-CO)3 ] 15 1833 (br)
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

dirhodium tricarbonyls [(RhTx)2 (m-CO)3 ] {Tx = HB(taz)2 (pz)

13, HB(taz)2 (pzMe2 ) 14, HB(taz)(pz)2 15} (Table 3). Subsequent
addition of one equivalent of PR3 to the CH2 Cl2 solutions
of the rhodium carbonyls gave [Rh(CO)(PPh3 ){HB(taz)2 (pz)}]
16, [Rh(CO)(PR3 ){HB(taz)2 (pzMe2 )}] (R = Cy 17, NMe2 18,
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Ph 19, OPh 20), [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 and
[Rh(CO)(PPh3 ){HB(taz)(pz)2 }] 22 which were isolated as yellow-
orange solids and characterised by elemental analysis, IR

Scheme 2

11618 | Dalton Trans., 2010, 39, 11616–11627 This journal is © The Royal Society of Chemistry 2010
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Table 4 Analytical and IR spectroscopic data for rhodium heteroscorpionate complexes

Analysis / %a
Complex Colour Yield / % C H N n(CO) / cm-1

[Rh(cod){HB(taz)2 (pz)}] 5 yellow-orange 44 44.0 (43.9) 5.5 (5.6) 19.8 (19.5) —

[Rh(cod){HB(taz)2 (pzMe2 )}] 6 yellow-orange 81 46.0 (45.9) 6.0 (6.0) 18.8 (18.6) —
[Rh(cod){HB(taz)2 (pzPh )}] 7 yellow 61 50.1 (49.9) 5.5 (5.6) 17.0 (17.2) —
[Rh(cod){HB(taz)(pz)2 }] 8 yellow-orange 51 45.8 (45.7) 5.4 (5.5) 19.6 (19.6) —
[Rh(CO)(PPh3 ){HB(taz)2 (pz)}] 16 yellow-orange 63 50.7 (50.8) 4.7 (4.7) 14.9 (14.8) 1978
[Rh(CO)(PCy3 ){HB(taz)2 (pzMe2 )}] 17 yellow 74 51.0 (50.9) 7.1 (7.2) 13.9 (14.0) 1963
[Rh(CO){P(NMe2 )3 }{HB(taz)2 (pzMe2 )}] 18 yellow-orange 35 38.6 (38.5) 6.3 (6.2) 22.3 (22.5) 1973
[Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}] 19 yellow-orange 64 51.9 (52.1) 4.7 (5.0) 14.3 (14.3) 1981
[Rh(CO){P(OPh)3 }{HB(taz)2 (pzMe2 )}] 20 yellow-orange 25 49.1 (49.1) 5.0 (4.7) 13.8 (13.5) 2010
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

[Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 yellow 77 54.5 (54.8) 4.8 (4.7) 13.5 (13.5) 1980
[Rh(CO)(PPh3 ){HB(taz)(pz)2 }] 22 yellow 61 53.1 (52.9) 4.5 (4.4) 14.2 (14.4) 1988
[Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}] 23 orange 13 36.5 (36.4) 5.1 (4.9) 21.5 (21.3) —
a
Calculated values in parentheses.

spectroscopy (Table 4) and multinuclear variable temperature

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NMR spectroscopy (Table 5).

Two isomers, with different coordination modes for the het-
eroscorpionate ligand, were observed for each of the rhodium
dicarbonyls 9, 11 and 12, as also seen for [Rh(CO)2 Tt].10 The
isomers can be assigned as having either k3 -coordination of
the heteroscorpionate (9b, 11b and 12b) or k2 -coordination (9a,
11a and 12a, along with 10) on the basis of their IR carbonyl
spectra. While such spectra allow the number of coordinated
donor atoms of the scorpionates to be deduced,8,10,13 they do not
permit those atoms (i.e. N or S) to be identified. (In neither the
solid state nor concentrated solution could n(B–H) absorptions
be detected for any of the complexes reported herein though
such absorptions can be used to distinguish between scorpionate
isomers.14 ) Moreover, dirhodium tricarbonyls [(RhTx)2 (m-CO)3 ]
are observed in equilibrium with the mononuclear dicarbonyl
complexes for three of the heteroscorpionate ligands; such a
binuclear species was not seen for HB(taz)2 (pzPh ), perhaps because
of the bulky phenyl substituent.
Attempts to synthesise the norbornadiene analogue of 6, i.e.
Fig. 1 The molecular structure of [Rh(cod){HB(taz)(pz)2 }] 8. Thermal
[Rh(nbd){HB(taz)2 (pzMe2 )}], by reacting stoichiometric amounts ellipsoids for this structure, and all others shown in this paper, are drawn
of [{Rh(nbd)(m-Cl)}2 ] with K+ 2- in CH2 Cl2 gave a mixture at the 50% probability level.
of products only one of which was isolated by column chro-
matography, i.e. an orange solid characterised by X-ray crys- All of the rhodium(I) heteroscorpionate complexes 6, 8, 10,
tallography (see below) as the heteroscorpionate rhodaboratrane 16, 18, 19 and 21 contain a broadly square planar rhodium
[Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}] 23. centre bound to a k2 -coordinated heteroscorpionate and the
ancillary ligands. However, the arrangement of those ligands in
the square plane varies according to the coordination mode of
The X-ray structures of complexes 6, 8, 10, 16–19, 21 the heteroscorpionate (S- and/or N-donation), the steric bulk of
and 23. In order to explore the effects of the scorpionate the pyrazolyl ring substituent(s) and the nature of the ancillary
and ancillary ligands on structure and isomer distribution ligands.
X-ray diffraction studies were carried out on [Rh(cod)Tx] The complex [Rh(cod){HB(taz)(pz)2 }] 8 (Fig. 1) has the
{Tx = HB(taz)2 (pzMe2 ) 6, HB(taz)(pz)2 8}, [Rh(CO)2 {HB(taz)2 - N 2 S-donor heteroscorpionate coordinated to rhodium through
(pzMe2 )}] 10, [Rh(CO)(PPh3 ){HB(taz)2 (pz)}] 16, [Rh(CO)(PR3 )- the nitrogen atoms of the two pyrazolyl rings with the B–H
{HB(taz)2 (pzMe2 )}] (R = Cy 17, NMe2 18, Ph 19), bond directed away from the rhodium square plane. The struc-
[Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 and [Rh{B(taz)2 (pzMe2 )}- ture is therefore comparable with those of tris(pyrazolyl)borate
{HB(taz)2 (pzMe2 )}] 23 using crystals grown by slow diffusion of rhodium(I) diene complexes such as [Rh(cod)TpMe2 ]. (The complex
n-hexane into a concentrated CH2 Cl2 solution of each complex at [Rh(cod)Tp] is trigonal bipyramidal in the solid state.15 ) Although
5 ◦ C. The structures of 6, 8, 16, 18, 19, 21 and 23 are shown in Fig. the nitrogen atom, N(6), of the thioxotriazolyl ring is positioned
1–7 (those of 10 and 17 are shown in the ESI) with selected bond above the rhodium centre it is too far away (3.280 Å), and in an
lengths and angles in Table 6 (and Table 7 for 23). unfavourable orientation, to be considered bonding.

This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 11616–11627 | 11619

Table 5 Proton, 13 C-{1 H}, 31 P-{1 H} and 11 B-{1 H} NMR spectroscopic data for rhodium heteroscorpionate complexesa
1 13
Complex H C-{1 H}
[Rh(cod){HB(taz)2 - 8.24 (br s, 1H, pz 5-H), 7.41 (s, 1H, pz
(pz)}] 5 3-H), 6.20 (dd, 1H, 1 J HH 1.9, 1 J HH 1.9, pz
4-H), 4.15 (br s, 4H, cod CH), 4.00 (br s,
4H, taz 4-CH 2 CH3 ), 2.56 (br s, 4H, cod
CHH exo ), 2.35 (s, 6H, taz 3-CH 3 ), 1.91
(br m, 4H, cod CHH endo ), 1.29 (br t, 6H,
3
J HH 7.0, taz 4-CH2 CH 3 )
[Rh(cod){HB(taz)2 - 5.80 (s, 1H, pz 4-H), 4.12 (br s, 4H, cod
(pzMe2 )}] 6 CH), 3.98 (q, 4H, 3 J HH 7.3, 4-CH 2 CH3 ),
2.45 (s, 3H, pz 3/5-CH 3 ), 2.33 (s, 9H, pz
3/5-CH 3 & taz 3-CH 3 ), 2.32 (br s, 4H,
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A
cod CHH exo ), 1.79 (q, 4H, J HH 7.9, cod
CHH endo ), 1.27 (t, 6H, 3 J HH 7.3, taz
4-CH2 CH 3 )
[Rh(cod){HB(taz)2 - 8.41 (d, 1H, 3 J HH 2.2, pz 5-H), 8.18 (br s,
(pzPh )}] 7 2H, pz 3-Ph), 7.45 (t, 2H, J HH 7.5, pz
3-Ph), 7.33 (t, 1H, J HH 7.5, pz 3-Ph), 6.53
(d, 1H, 3 J HH 2.2, pz 4-H), 4.11 (br s, 4H,
cod CH), 4.05 (dq, 2H, 2 J HH 14.3, 3 J HH
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7.2, taz 4-CHHCH3 ), 3.94 (dq, 2H, 2 J HH
14.3, 3 J HH 7.2, taz 4-CHHCH3 ), 2.56 (br
m, 4H, cod CHH exo ), 2.34 (s, 6H, taz
3-CH 3 ), 1.85 (br d, 4H, J HH 8.1, cod
CHH endo ), 1.28 (t, 6H, 3 J HH 7.2, taz
4-CH2 CH 3 )
[Rh(cod){HB(taz)- 7.83 (d, 2H, 3 J HH 1.8, pz 5-H), 7.43 (d,
(pz)2 }] 8 2H, 3 J HH 1.8, pz 3-H), 6.26 (br s, 2H, pz
4-H), 4.16 (br s, 4H, cod CH), 4.06 (q,
2H, 3 J HH 7.2, taz 4-CH 2 CH3 ), 2.44 (s, 3H,
taz 3-CH 3 ), 2.33 (br m, 4H, cod CHH exo ),
1.88 (q, 4H, J HH 8.4, cod CHH endo ), 1.31
(t, 3H, 3 J HH 7.2, taz 4-CH2 CH 3 )b
[Rh(CO)(PPh3 )- 8.10 (d, 1H, 3 J HH 2.6, pz 5-H), 7.87-7.29
{HB(taz)2 (pz)}] 16 (m, 15H, PPh3 ), 6.49 (d, 1H, 3 J HH 2.2 pz
3-H), 5.81 (dd, 1H, 3 J HH 2.6, 3 J HH 2.2 pz
4-H), 4.39 (dq, 1H, 2 J HH 13.8, 3 J HH 7.1,
taz 4-CHHCH3 ), 4.08 (dq, 1H, 2 J HH 14.2,
3
J HH 7.1, taz 4-CHHCH3 ), 3.94 (dq, 1H,
2
J HH 14.2, 3 J HH 7.1, taz 4-CHHCH3 ),
3.93 (dq, 1H, 2 J HH 13.8, 3 J HH 7.1, taz
4-CHHCH3 ), 2.48 (s, 3H, taz 3-CH 3 ),
2.32 (s, 3H, taz 3-CH 3 ), 1.40 (t, 3H, 3 J HH
7.1, taz 4-CH2 CH 3 ), 1.34 (t, 3H, 3 J HH 7.1,
taz 4-CH2 CH 3 )c
[Rh(CO)(PCy3 ){HB- 5.86 (s, 1H, pz 4-H), 4.00 (q, 4H, 3 J HH
(taz)2 (pzMe2 )}] 17 7.2, taz 4-CH 2 CH3 ), 2.41 (s, 3H, pz
5-CH 3 ), 2.32 (br s, 9H, taz 3-CH 3 & pz
5-CH 3 ), 2.16-1.19 (br m, 33H, PCy3 ),
1.29 (t, 6H,3 J HH 7.2, taz 4-CH2 CH 3 )
[Rh(CO){P(NMe2 )3 }- 5.84 (s, 1H, pz 4-H), 3.99 (q, 4H, 3 J HH
{HB(taz)2 (pzMe2 )}] 18 7.3, taz 4-CH 2 CH3 ), 2.63 (d, 18H, 3 J HP
10.3, P{N(CH 3 )2 }3 ), 2.39 (br s, 6H, pz
3,5-CH 3 ), 2.33 (s, 6H, taz 3-CH 3 ), 1.28 (t,
6H, 3 J HH 7.3, taz 4-CH2 CH 3 )
[Rh(CO)(PPh3 )- 7.67-7.26 (m, 15H, PPh3 ), 5.68 (br s, 1H,
{HB(taz)2 (pzMe2 )}] 19 pz 4-H), 3.73 (br s, 4H, taz 4-CH 2 CH3 ),
2.41 (br s, 3H, pz 5-CH 3 ), 2.10 (br s, 9H,
taz 3-CH 3 & pz 5-CH 3 ), 1.30 (br t,
6H,3 J HH 7.0, taz 4-CH2 CH 3 )
[Rh(CO){P(OPh)3 }- 7.37-7.11 {m, 15H, P(OPh)3 }, 5.82 (s, 1H,
{HB(taz)2 (pzMe2 )}] 20 pz 4-H), 3.68 (br m, 4H, taz 4-CH 2 CH3 ),
2.38 (br s, 3H, pz 5-CH 3 ), 2.32 (s, 6H, taz
3-CH 3 ), 2.04 (s, 3H, pz 5-CH 3 ), 1.15 (br
t, 6H,3 J HH 7.0, taz 4-CH2 CH 3 )
11620 | Dalton Trans., 2010, 39, 11616–11627
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31
P-{1 H} 11
B-{1 H}
148.91 (br s, taz C 3 ), 140.12 (s, pz C 3/5 ), — -4.34 {s,
135.85 (br s, pz C 3/5 ), 106.66 (br s, pz C 4 ), HB(taz)2 (pz)}
80.93 (br s, cod CH), 39.89 (s, taz
4-CH2 CH3 ), 31.59 (br s, cod CH2 ), 13.75
(s, taz 3-CH3 ), 11.62 (s, taz 4-CH2 CH3 )
167.22 (br s, taz C 5 ), 149.24 (s, pz C 3/5 ), — -4.58 {s,
148.76 (s, taz C 3 ), 146.71 (s, pz C 3/5 ), HB(taz)2 (pz)}
107.51 (br s, pz C 4 ), 80.18 (br s, cod CH),
39.96 (s, taz 4-CH2 CH3 ), 31.68 (br s, cod
CH2 ), 15.10 (s, pz 3/5-CH3 ), 14.01 (s, taz
3-CH3 ), 13.68 (s, pz 3/5-CH3 ), 11.72 (s,
taz 4-CH2 CH3 )
151.96 (s, pz C 3/5 ), 149.52 (s, taz C 3 ), — -3.61 {s,
136.90 (s, pz C 3/5 ), 128.60 (s, pz 3-Ph), HB(taz)2 (pz)}
127.67 (s, pz 3-Ph), 127.00 (br s, pz 3-Ph),
100.36 (s, pz C 4 ), 80.09 (br s, cod CH),
40.08 (s, taz 4-CH2 CH3 ), 31.74 (br s, cod
CH2 ), 13.79 (s, taz 3-CH3 ), 11.59 (s, taz
4-CH2 CH3 )
169.41 (br s, taz C 5 ), 147.64 (br s, taz C 3 ), — -4.34 {s,
139.96 (s, pz C 3/5 ), 138.64 (s, pz C 3/5 ), HB(pz)2 (taz)}
105.37 (s, pz C 4 ), 81.29 (d, 1 J CRh 12.1, cod
CH), 39.91 (s, taz 4-CH2 CH3 ), 30.91 (s,
cod CH2 ), 13.84 (s, taz 3-CH3 ), 11.87 (s,
taz 4-CH2 CH3 )
134.89-128.56 (m, pz C 5 & PPh3 ), 106.61 41.18 (d, -4.49 {s,
(br s, pz C 4 ), 40.06 (s, taz 4-CH2 CH3 ), 1
J PRh 159.1, HB(taz)2 (pz)}
13.93 (s, taz 3-CH3 ), 11.75 (s, taz PPh3 )c
4-CH2 CH3 )
106.40 (br s, pz C 3 ), 39.69 (v.br s, taz 50.53 (br d, -4.53 {s,
4-CH2 CH2 ), 28.28-26.56 (m, PCy3 ), 1
J PRh 146.1, HB(taz)2 (pz)}
14.31 (s, pz 3/5-CH3 ), 13.99 (s, pz PCy3 )
3/5-CH3 ), 13.92 (s, taz 3-CH3 ), 11.62 (s,
taz 4-CH2 CH3 )
166.57 (br s, taz C 5 ), 150.15 (br s, pz C 5 ), 128.43 {d, -4.46 {s,
148.23 (s, taz C 3 ), 147.44 (br s, pz C 5 ), 1
J PRh 194.5, HB(taz)2 (pz)}
106.70 (br s, pz C 4 ), 39.55 (s, taz P(NMe2 )3 }
4-CH2 CH3 ), 38.93 (d, 2 J CP 6.3,
P{N(CH3 )2 }3 ), 15.76 (br s, pz 3/5-CH3 ),
13.96 (s, pz 3/5-CH3 ), 13.86 (s, taz
3-CH3 ), 11.69 (s, taz 4-CH2 CH3 )
134.86-128.59 (m, pz C 3/5 & PPh3 ), 39.72 41.55 (br d, -5.00 {s,
(s, taz 4-CH2 CH3 ), 13.94 (s, taz 3-CH3 ), 1
J PRh 168.4, HB(taz)2 (pz)}
11.66 (s, taz 4-CH2 CH3 ) PPh3 )
152.40 (br s, pz C 5 ), 130.78-120.93 {m, pz 120.63 {d, -4.83 {s,
C 3/5 & P(OPh)3 }, 39.57 (s, taz 1
J PRh 262.4, HB(taz)2 (pz)}
4-CH2 CH3 ), 14.36 (s, pz 3/5-CH3 ), 14.11 P(OPh)3 }
(br s, taz 3-CH3 ), 14.01 (s, pz 3/5-CH3 ),
11.57 (s, taz 4-CH2 CH3 )
This journal is © The Royal Society of Chemistry 2010
 View Online

Table 5 (Contd.)

1 13
Complex H C-{1 H} 31
P-{1 H} 11
B-{1 H}

[Rh(CO)(PPh3 ){HB-
(taz)2 (pzPh )}] 21
[Rh(CO)(PPh3 ){HB-
(taz)(pz)2 }] 22
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A
8.25 (br s, 1H, pz 5-H), 7.95-7.16 (m, 134.84-128.25 (m, pz C 5 & pz 3-Ph & 41.39 (v.br s, -4.14 {s,
20H, PPh3 & pz 3-Ph), 6.31 (v.br s, 1H, PPh3 ), 40.25 (s, taz 4-CH2 CH3 ), 13.97 (s, PPh3 ) HB(taz)2 (pz)}
pz 4-H), 3.91 (br s, 4H, taz 4-CH 2 CH3 ), taz 3-CH3 ), 11.69 (s, taz 4-CH2 CH3 )
2.31 (s, 6H, taz 3-CH 3 ), 1.26 (br s, 6H,
taz 4-CH2 CH 3 )
7.84 (d, 2H, 3 J HH 2.2, pz 5-H), 7.55-7.32 191.00 (dd, 1 J CRh 72.6, 2 J CP 21.9, CO), 44.74 (d, -4.56 {s,
(m, 15H, PPh3 ), 7.13 (br s, 2H, pz 3-H), 169.58 (s, taz C 5 ), 147.65 (s, taz C 3 ), 1
J PRh 159.1, HB(pz)2 (taz)}
6.06 (dd, 2H, 3 J HH 2.2,3 J HH 2.2, pz 4-H), 143.79 (s, pz C 3/5 ), 138.52 (s, pz C 3/5 ), PPh3 )
3.94 (q, 2H,3 J HH 7.3, taz 4-CH 2 CH3 ), 134.85-128.93 (m, PPh3 ), 105.25 (s, pz
1.93 (s, 3H, taz 3-CH 3 ), 1.20 (t, 3H, 3 J HH C 4 ), 39.32 (s, taz 4-CH2 CH3 ), 13.95 (s,
7.3, taz 4-CH2 CH 3 ) taz 3-CH3 ), 11.39 (s, taz 4-CH2 CH3 )

[Rh{B(taz)2 (pzMe2 )}-
{HB(taz)2 (pzMe2 )}] 23
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5.87 (s, 1H, pz 4-H), 5.68 (s, 1H, pz 4-H),
4.60 (v.br s, 1H, BH), 4.22 (br m, 1H, taz
4-CHHCH3 ), 4.03 (br m, 2H, taz
4-CHHCH3 ), 3.88 (br m, 2H, taz
4-CHHCH3 ), 3.72 (br m, 2H, taz
4-CHHCH3 ), 3.55 (br m, 1H, taz
4-CHHCH3 ), 2.33 (br s, 6H, taz 3-CH 3 ),
2.32 (s, 6H, taz 3-CH 3 ), 2.31 (br s, 3H, pz
173.64 (s, taz C 5 ), 172.12 (s, taz C 5 ), — -0.18 (br s),
153.86 (s, taz C 3 ), 148.31 (s, pz C 3/5 ), -1.97 (v.br s)d
143.64 (s, pz C 3/5 ), 107.32 (s, pz C 4 ),
106.63 (s, pz C 4 ), 39.27 (s, taz
4-CH2 CH3 ), 15.82 (s, pz 3/5-CH3 ), 14.18
(s, taz 3-CH3 ), 13.22 (s, pz 3/5-CH3 ),
11.76 (s, taz 4-CH2 CH3 )d

3/5-CH 3 ), 2.28 (s, 3H, pz 3/5-CH 3 ), 2.26

(br s, 3H, pz 3/5-CH 3 ), 2.13 (s, 3H, pz
3/5-CH 3 ), 1.30 (t, 6H, 3 J HH 7.2, taz
4-CH2 CH 3 ), 1.22 (br t, 6H, 3 J HH 7.2, taz
4-CH2 CH 3 )d
a
Chemical shift (d) in ppm, J values in Hz, spectra in CD2 Cl2 at 20 ◦ C unless otherwise stated. b At -20 ◦ C. c At -60 ◦ C. d In CDCl3 .

Table 6 Selected bond lengths (Å) and angles (◦ ) for [Rh(cod){HB(taz)2 (pzMe2 )}] 6, [Rh(cod){HB(taz)(pz)2 }] 8, [Rh(CO)2 {HB(taz)2 (pzMe2 )}] 10,
[Rh(CO)(PPh3 ){HB(taz)2 (pz)}] 16, [Rh(CO)(PCy3 ){HB(taz)2 (pzMe2 )}] 17, [Rh(CO){P(NMe2 )3 }{HB(taz)2 (pzMe2 )}] 18, [Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}]
19 and [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21

6 8 10 16 17 18 19 21

Rh(1)–X(1)a 1.965 2.011 1.837(3) 1.824(3) 2.281(1) 2.244(1) 1.813(3) 1.820(3)

Rh(1)–X(2)b 2.028 2.005 1.868(3) 2.258(1) 1.821(2) 1.828(4) 2.268(1) 2.255(1)
Rh(1)–Y(1)c 2.382(1) 2.110(2) 2.361(1) 2.394(1) 2.401(1) 2.396(1) 2.384(1) 2.392(1)
Rh(1)–Y(2)d 2.139(2) 2.081(2) 2.076(2) 2.095(2) 2.104(2) 2.128(3) 2.084(3) 2.445(1)
Rh(1) ◊ ◊ ◊ Y(3)e 4.562(1) 3.280(3) 3.384(2) 5.181(1) 3.475(3) 3.432(2) 3.145(3) 4.489(2)
Rh(1) ◊ ◊ ◊ Y(4)f — 5.568(1) 4.040(1) — 4.535(1) 4.342(2) 5.373(1) —
Rh(1) ◊ ◊ ◊ B(1) 3.055(3) 3.328(3) 3.335(3) 3.213(3) 3.460(3) 3.454(4) 3.445(3) 3.099(3)
B(1)–N(a)g 1.557(3) 1.539(4) 1.562(3) 1.559(3) 1.560(3) 1.558(5) 1.561(4) 1.535(4)
B(1)–N(b)h 1.543(3) 1.535(4) 1.539(3) 1.550(3) 1.539(3) 1.531(4) 1.537(4) 1.552(3)
B(1)–N(c)i 1.532(3) 1.546(3) 1.561(3) 1.527(3) 1.549(3) 1.558(4) 1.541(4) 1.526(4)
N(a)–B(1) ◊ ◊ ◊ Rh(1)–Y(1) 7.1(1) 3.3(1) -4.1(1) 2.6(1) 3.2(1) 0.9(2) 15.8(1) 9.1(1)
N(b)–B(1) ◊ ◊ ◊ Rh(1)–Y(2) 3.9(1) 6.6(1) 3.9(1) 1.4(1) 3.7(1) -3.7(2) -2.2(1) 22.6(1)
N(c)–B(1) ◊ ◊ ◊ Rh(1) ◊ ◊ ◊ Y(3) 23.5(2) 23.3(1) -30.4(1) 35.7(3) 29.7(1) 29.9(1) 28.3(1) 16.7(2)
Y(3) ◊ ◊ ◊ N(c)–B(1) ◊ ◊ ◊ Rh(1) -29.4(2) -52.1(2) 96.0(2) -45.1(4) -90.6(2) -92.8(3) -64.8(2) -33.8(3)
a
X(1): 6, midpoint of C(23)–C(24); 8, midpoint of C(14)–C(15); 10, 16, 19, 21, C(1); 17, 18, P(1). b X(2): 6, midpoint of C(19)–C(20); 8, midpoint of
C(18)–C(19); 10, C(2); 16, 19, 21, P(1); 17, 18, C(1). c Y(1): 6, 10, 16–19, 21, S(1); 8, N(4). d Y(2): 6, 8, 10, 16–19, N(2); 21, S(2). e Y(3): 6, 16, S(2); 8, N(6);
10, 17–19, N(7); 21, N(8). f Y(4): 8, S(1); 10, 17–19, S(2). g N(a): 6, 8, 10, 16–19 N(3); 21, N(1). h N(b): 6, 8, 10, 16–19, N(1); 21, N(4). i N(c): 6, 10, 16–19,
N(6); 8, N(5); 21, N(7).

By contrast the S2 N-donor heteroscorpionate in [Rh(cod){HB-
(taz)2 (pzMe2 )}] 6 (Fig. 2) adopts a k2 [SN]-coordination mode, with
the B–H bond directed towards the metal in a B–H ◊ ◊ ◊ Rh inter-
action (i.e. as in rhodium(I) Tm9 and Tt10 complexes.), implying
that coordination of the harder nitrogen donor is favoured over
the softer sulfur donors in the solid state.
The rhodium carbonyl triphenylphosphine complexes
[Rh(CO)(PPh3 ){HB(taz)2 (pz)}] 16 (Fig. 3) and [Rh(CO)(PPh3 )-
{HB(taz)2 (pzMe2 )}] 19 (Fig. 4) have the heteroscorpionate ligand
k2 [SN]-coordinated, with the pyrazolyl ring cis to PPh3 . However,
they differ in the relative orientations of the uncoordinated
thioxotriazolyl ring and the B–H bond; the B–H bond is directed
towards rhodium in 16 but away from the metal in 19. (The two
structures are related by inversion of the seven-membered ring
linking the rhodium centre and boron bridgehead.)
The third structurally characterised PPh3 complex, namely
[Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 (Fig. 5), is unique in having
the heteroscorpionate k2 [S2 ]-coordinated with the B–H bond
directed towards rhodium, as in [Rh(CO)(PPh3 )Tt].10 Adoption
of the k2 [NS]-coordination found in 16 and 19 is most likely
disfavoured by steric hinderance between PPh3 and the phenyl
substituent of the pyrazolyl ring.
The complexes [Rh(CO)(PR3 ){HB(taz)2 (pzMe2 )}] (R = Cy 17,
NMe2 18) (see Fig. 6 for 18 and the ESI for 17) have the same

This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 11616–11627 | 11621

Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A
Fig. 2 The molecular structure of [Rh(cod){HB(taz)2 (pzMe2 )}] 6.
Downloaded by Bristol University on 05 March 2011
Fig. 3 The molecular structure of [Rh(CO)(PPh3 ){HB(taz)2 (pz)}] 16.
scorpionate coordination mode as the PPh3 analogue 19. However,
the positions of the ancillary ligands vary; the phosphines of 17
and 18 are trans to the nitrogen donor of the scorpionate whereas
PPh3 is bound trans to sulfur in 19. That PCy3 and P(NMe2 )3
are stronger electron donors than PPh3 implies that an electronic
effect leads to the different structures. The cone angles of PPh3 and
P(NMe2 )3 are very similar (145 and 157◦ respectively16 ) making a
steric explanation less likely.
The structure of the dicarbonyl [Rh(CO)2 {HB(taz)2 (pzMe2 )}] 10
(see the ESI) was determined using a single crystal obtained by
slowly diffusing n-hexane into a CH2 Cl2 solution containing a
mixture of 10 and 14. In this case the heteroscorpionate is k2 [NS]-
coordinated with the uncoordinated taz ring pseudo-parallel to the
rhodium square plane, as in 19.
Finally, the molecular structure of [Rh{B(taz)2 (pzMe2 )}-
{HB(taz)2 (pzMe2 )}] 23 (Fig. 7, Table 7) has an octahedral rhodium
atom k3 [BS2 ]-bound to a boratrane fragment (formed by B–
H activation of one heteroscorpionate ligand) and a k3 [S2 N]-
coordinated heteroscorpionate; the Rh–N bond trans to boron
is elongated (2.50 Å, cf . 2.1–2.2 Å in [Rh(cod)TpMe2 ]15 ) be-
cause of the pronounced trans influence of the Rh–B bond.
The bond lengths and angles of the rhodaboratrane unit are
comparable with those of other, Tt-derived, rhodaboratranes, i.e.
11622 | Dalton Trans., 2010, 39, 11616–11627
View Online
Fig. 4 The molecular structure of [Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}] 19.
Fig. 5 The molecular structure of [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21.
[Rh(CO)(PR3 ){B(taz)3 }]+ ,10 and the k3 [BS2 ]-coordinated iridabo-
ratrane [Ir(CO)(PPh3 )H{B(mtMe )2 H}].11
NMR spectroscopy and fluxional behaviour. The 1 H NMR
spectra of [Rh(cod){HB(taz)(pz)2 }] 8 and [Rh(CO)(PPh3 ){HB-
(taz)(pz)2 }] 22 were obtained at a range of temperatures, with
-20 and +20 ◦ C respectively giving optimal quality. The spectrum
of 8 shows the two pyrazolyl rings to be equivalent, consistent
with the X-ray structure where only the two pyrazolyl rings are
coordinated to rhodium. The two pyrazolyl rings of 22 are also
equivalent at room temperature but inequivalent at -80 ◦ C (the
resonances of the thioxotriazolyl ring are unchanged) implying
dynamic ring-exchange in solution. However, the scorpionate
coordination mode cannot be identified from the spectrum alone.
The room temperature 1 H NMR spectrum of
[Rh(cod){HB(taz)2 (pz)}] 5 shows two equivalent thioxotriazolyl
rings but, on lowering the temperature, these rings become
distinguishable while there are negligible changes in the
resonances of the pyrazolyl ring. Again, the coordinated
and uncoordinated thioxotriazolyl rings exchange while the
pyrazolyl ring remains coordinated, i.e. the heteroscorpionate is
This journal is © The Royal Society of Chemistry 2010
 View Online

Table 7 Selected bond lengths (Å) and angles (◦ ) for [Rh{B(taz)2 -

(pzMe2 )}{HB(taz)2 (pzMe2 )}] 23

Rh(1)–B(1) 2.136(7) B(2)–N(10) 1.545(9)

Rh(1)–S(1) 2.364(2) B(2)–N(11) 1.564(9)
Rh(1)–S(2) 2.374(2) B(2)–N(14) 1.546(9)
Rh(1) ◊ ◊ ◊ N(2) 3.798(6)
Rh(1)–S(3) 2.341(2) N(3)–B(1)–Rh(1)-S(1) -24.5(3)
Rh(1)–S(4) 2.359(2) N(6)–B(1)–Rh(1)-S(2) -5.8(4)
Rh(1)–N(9) 2.501(5) N(11)–B(2) ◊ ◊ ◊ Rh(1)-S(3) -32.8(3)
Rh(1) ◊ ◊ ◊ B(2) 3.728(7) N(14)–B(2) ◊ ◊ ◊ Rh(1)-S(4) -40.2(3)
B(1)–N(1) 1.555(8) N(2)–N(1)–B(1)–Rh(1) 79.4(6)
B(1)–N(3) 1.531(8) Q(1)a ◊ ◊ ◊ N(9)–Rh(1) 126.64
B(1)–N(6) 1.551(8)
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

a
Q(1): midpoint of C(16)–C(17).

Fig. 6 The molecular structure of [Rh(CO){P(NMe2 )3 }{HB(taz)2 - matching either k2 [SN]- or k2 [S2 ]-coordination modes of the
(pzMe2 )}] 18. heteroscorpionate ligand; the former is the structure observed in
the solid state. The coordinated and uncoordinated thioxotriazolyl
Downloaded by Bristol University on 05 March 2011

rings are also distinguished at low temperature. For example, the

Fig. 7 The molecular structure of [Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}]
23.
k2 [SN]-coordinated. By comparing the methyl resonances of the
thioxotriazolyl rings with those of [Rh(cod)Tt] 10 the coordinated
(d H 2.30, 1.26 ppm) and uncoordinated (d H 2.50, 1.35 ppm)
proton resonances can be identified.
The 1 H and 31 P NMR spectra of [Rh(CO)(PPh3 ){HB(taz)2 (pz)}]
16 are broad at room temperature but fully resolved at -60 ◦ C with
the resonances consistent with the k2 [SN]-/N-cis-PPh3 structure
observed in the solid state. The protons in the three- and four-
positions of the pyrazolyl ring of 7 have lower chemical shifts (3-H
by ca. 1 ppm, 4-H by ca. 0.5 ppm) than those of the cod analogue
5 because of the shielding of the PPh3 ligand coordinated cis to the
pyrazolyl ring, an effect also observed for one of the thioxotriazolyl
rings in [Rh(CO)(PPh3 )Tt].10
The room temperature NMR spectra of [Rh(cod){HB-
(taz)2 (pzMe2 )}] 6, showing equivalent thioxotriazolyl rings, are
inconsistent with the k2 [SN]-mode observed in the solid state.
However, the low temperature 1 H NMR spectra showed that
the pyrazolyl and thioxotriazolyl rings interchange, resulting in
an equilibrium between coordination isomers. The presence of
two isomers is most clearly shown at -60 ◦ C by two signals,
in a 7 : 3 ratio, for the pyrazolyl 4-H proton (d H 5.82, 5.71
ppm). These correspond to bound and unbound pyrazolyl rings,
resonance of the 3-CH2 CH 3 protons of the uncoordinated ring
is at d H 1.24 ppm while those of the coordinated rings (for both
isomers) give a broad signal at d H 1.15 ppm (see the ESI for full
spectral assignment).
As with 6, the variable temperature 1 H NMR spectra of
[Rh(cod){HB(taz)2 (pzPh )}] 7 (Fig. 8) revealed rapid exchange
between two isomers. At -80 ◦ C the isomers (in a 1 : 1 ratio)
give well resolved resonances for the pyrazolyl rings († and ‡)
and distinct signals for equivalent (k2 [S2 ]-)‡ and inequivalent
(k2 [SN]-)† thioxotriazolyl rings.
The variable temperature NMR spectra of [Rh(CO)(PPh3 )-
{HB(taz)2 (pzPh )}] 21 also revealed dynamic interchange of pyra-
zolyl and thioxotriazolyl rings, and two isomers in a 1 : 1 ratio
at low temperature, e.g. the 31 P-{1 H} NMR spectrum at -60 ◦ C
showed two resonances, at d P 42.51 (d, 1 J PRh 147.9, PPh3 ) and d P
38.88 (d, 1 J PRh 160.0, PPh3 ). (Details of the near full assignment
of the 1 H spectrum at -60 ◦ C for both isomers are given in the
ESI.) One isomer has a k2 [S2 ]-coordinated heteroscorpionate (as
in the solid state structure) while the other is k2 [SN]-coordinated
with the pyrazolyl ring cis to PPh3 . (The latter, analogous to the
solid state structure of 16, is based on a distinctive low chemical
shift for the 4-H proton on the pyrazolyl ring, due to shielding by
the adjacent phenyl rings of the PPh3 ligand, as also observed for
16.)
The variable temperature 1 H and 31 P NMR spectra of
[Rh(CO)(PR3 ){HB(taz)2 (pzMe2 )}] (R = Cy 17, NMe2 18, Ph 19,
OPh 20) show evidence of interchange of multiple isomers for
18–20. However, the only dynamic process observed for 17
is interchange of two inequivalent thioxotriazolyl rings of a
single isomer. The presence of multiple isomers of 18–20 at low
temperatures is clearly observed in the 31 P NMR spectrum and
for the pyrazolyl 4-H signals in the 1 H NMR spectrum. Thus, at
-80 ◦ C the spectrum of 18 showed at least two isomers 18a {d H 5.91
(s, 1H, pz 4-H), d P 132.32 (d, 1 J PRh 191 Hz, P(NMe2 )3 )} and 18b
{d H 5.79 (s, 1H, pz 4-H), d P 121.41 (d, 1 J PRh 207 Hz, P(NMe2 )3 )}
in a 3 : 2 ratio. Similarly, the 31 P-{1 H} spectrum of 19 at -90 ◦ C
showed two isomers, 19a {d P 42.96 (d, 1 J PRh 152 Hz, PPh3 )} and
19b {d P 37.58 (d, 1 J PRh 167 Hz, PPh3 )} in a 7 : 3 ratio, and two
isomers of 20, 20a {d H 5.84 (s, 1H, pz 4-H), d P 116.23 (d, 1 J PRh
301 Hz, P(OPh)3 )} and 20b {d H 5.90 (s, 1H, pz 4-H), d P 122.73 (d,

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Fig. 8 Variable temperature 1 H NMR spectra of [Rh(cod){HB-
(taz)2 (pzPh )}] 7, showing two isomers († and ‡), residual CH 2 Cl2 /CHDCl2
(*) and trace H 2 O (§).
1
J PRh 259 Hz, P(OPh)3 )} were observed at -80 ◦ C in an 4 : 1 ratio.
Although the isomers observed for 18–20 cannot be conclusively
identified from the spectral data, they are likely to have k2 [S2 ]-
and k2 [SN]-coordinated heteroscorpionates, given the solid state
structures of 18 and 19, and the isomers observed for 6, 7 and 21.
1
The H NMR spectrum of [Rh{B(taz)2 (pzMe2 )}-
{HB(taz)2 (pz )}] 23 (Table 5) shows one sharp and one
Me2
broad signal for each environment of the pzMe2 /taz rings. The
broader signals most likely correspond to the [HB(taz)2 (pzMe2 )]-
heteroscorpionate fragment, and the sharper signals to the more
rigid bicyclo[3.3.0] cage of the boratrane, [Rh{B(taz)2 (pzMe2 )}]+ .
However, variable temperature NMR spectroscopy failed to
resolve the broadened signals which could have allowed for a
fuller assignment.
Isomer interchange. Although there are no quantitative data
{and the only comprehensive theoretical study has been on
rhodium(I) dicarbonyl TpR complexes13 } a qualitative mechanism
for the ring-exchange, and hence isomerisation, of rhodium(I)
heteroscorpionates can be described by extending that for
rhodium(I) Tt10 and Tp13 complexes. The mechanism, modified
to include the effect of inequivalent donor rings, and shown
for [RhLL¢{HB(taz)2 (pzR )}] in Scheme 3, can also be applied to
complexes of N 2 S-donor heteroscorpionates and can be simplified
for complexes where L = L¢.
There are three distinct square-pyramidal (SPY) isomers (where
the scorpionate is k3 [S2 N]-coordinated) which can interconvert
via trigonal bipyramidal (TBP) intermediates by Berry pseudoro-
tation. The axially bound donor ring of the SPY isomers can
detach to give square planar isomers with an uncoordinated donor
ring pseudo-parallel to the square plane (SP1), as observed in the
solid state structure of 19 (SP1-SN, S-trans-CO). Inversion of the
six- (for k2 [N2 ]-coordination), seven- (for k2 [SN]-coordination)
or eight- (for k2 [S2 ]-coordination) membered ring linking the
rhodium atom and the boron bridgehead through the donor rings
leads to a second set of square planar isomers with the B–H bond
11624 | Dalton Trans., 2010, 39, 11616–11627
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Scheme 3
directed towards the metal centre (SP2), as found in the solid state
structures of 16 (SP2-SN, S-cis-CO) and 21 (SP2-SS).
Conclusions
The reaction of potassium heteroscorpionate salts with Rh(I)
precursors gave a series of square planar complexes the solid state
and solution structures of which depend on the steric and/or elec-
tronic properties of the heteroscorpionate and ancillary ligands.
Qualitative conclusions can be drawn relating to the observed
structural preferences.
(i) Two isomers in equilibrium are likely to have k2 [S2 ]- and
2
k [SN]-coordination (in the case of an S2 N-donor heteroscorpi-
onate), interchange requiring the exchange of only two donor rings
rather than all three.
(ii) In carbonyl phosphine complexes with k2 [SN]-coordinated
scorpionates, the stronger electron-donating PR3 ligands {i.e. PCy3
and P(NMe2 )3 } coordinate trans to nitrogen while the weaker
donors {i.e. PPh3 and P(OPh)3 } coordinate trans to sulfur.
(iii) For S2 N-donor heteroscorpionates k2 [S2 ]-coordination is
only favoured over k2 [SN]-coordination when steric factors dom-
inate, e.g. k2 [S2 ]-coordination is favoured in the solid state for
[Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 as unfavourable interactions
would occur between the phenyl ring-substituent and PPh3 in an
SP1-SN, N-cis-PPh3 structure.
(iv) SP2 isomers are only favoured over SP1 isomers for k2 [S2 ]-
coordinated scorpionates and k2 [SN]-coordinated heteroscorpi-
onates with minimal steric bulk, i.e. the energy barrier for inversion
is low enough for eight-membered B(NCS)2 Rh and sterically
unrestricted seven-membered B(NCS)(NN)Rh rings.
This journal is © The Royal Society of Chemistry 2010
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Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A

Table 8 Crystal and refinement data for [Rh(cod){HB(taz)2 (pzMe2 )}]·CH2 Cl2 6·CH2 Cl2 , [Rh(cod){HB(taz)(pz)2 }] 8, [Rh(CO)2 {HB(taz)2 (pzMe2 )}] 10, [Rh(CO)(PPh3 ){HB(taz)2 (pz)}]·2CH2 Cl2
16·2CH2 Cl2 , [Rh(CO)(PCy3 ){HB(taz)2 (pzMe2 )}]·2CHCl3 ·0.5C6 H14 17·2CHCl3 ·0.5C6 H14 , [Rh(CO){P(NMe2 )3 }{HB(taz)2 (pzMe2 )}]·0.5CH2 Cl2 18·0.5CH2 Cl2 , [Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}]·CH2 Cl2
19·CH2 Cl2 , [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}]·2CH2 Cl2 21·2CH2 Cl2 and [Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}]·4CH2 Cl2 23·4CH2 Cl2

[Rh(CO)(PPh3 )- [Rh(CO)(PCy3 )- [Rh(CO){P(NMe2 )3 }- [Rh(CO)(PPh3 )-

[Rh(cod){HB(taz)2 - {HB(taz)2 (pz)}]· {HB(taz)2 (pzMe2 )}]· {HB(taz)2 (pzMe2 )}]· [Rh(CO)(PPh3 )- {HB(taz)2 (pzPh )}]· [Rh{B(taz)2 (pzMe2 )}-
(pzMe2 )}]·CH2 Cl2 [Rh(cod){HB- [Rh(CO)2 {HB- 2CH2 Cl2 2CHCl3 ·0.5C6 H14 0.5CH2 Cl2 {HB(taz)2 (pzMe2 )}]· 2CH2 Cl2 {HB(taz)2 (pzMe2 )}]·
6·CH2 Cl2 (taz)(pz)2 }] 8 (taz)2 (pzMe2 )}] 10 16·2CH2 Cl2 17·2CHCl3 ·0.5C6 H14 18·0.5CH2 Cl2 CH2 Cl2 19·CH2 Cl2 21·2CH2 Cl2 4CH2 Cl2 23·4CH2 Cl2

Formula C24 H38 BCl2 N8 RhS2 C19 H27 BN7 RhS C17 H24 BN8 O2 RhS2 C34 H39 BCl4 N8 C39 H66 BCl6 N8 - C23 .5 H45 BCl3 N11 - C35 H41 BCl2 N8 - C40 H43 BCl4 N8 - C34 H55 B2 Cl8 -
OPRhS2 OPRhS2 OPRhS2 OPRhS2 OPRhS2 N16 RhS4

This journal is © The Royal Society of Chemistry 2010

M 687.36 499.26 550.28 926.34 1084.51 812.86 869.47 1002.43 1224.34
Crystal system Monoclinic Monoclinic Monoclinic Triclinic Triclinic Triclinic Triclinic Monoclinic Monoclinic
Space group P21 /c P21 /n P21 /n P1̄ P1̄ P1̄ P1̄ P21 /c P21 /c
a/Å 13.761(1) 14.635(1) 10.636(1) 11.374(1) 12.598(3) 10.888(2) 10.505(1) 14.946(1) 20.179(4)
b/Å 10.091(1) 10.109(1) 16.612(1) 13.004(1) 13.928(3) 12.172(2) 12.412(2) 16.777(1) 15.811(3)
c/Å 21.575(3) 15.154(1) 13.705(1) 14.721(1) 15.347(3) 13.906(3) 16.077(3) 17.634(1) 17.133(3)
a (◦ ) 90.00 90.00 90.00 82.70(1) 78.64(3) 92.35(3) 80.98(1) 90.00 90.00
b (◦ ) 93.25(1) 104.96(1) 100.89(1) 71.10(1) 72.48(3) 93.44(3) 74.95(1) 95.07(1) 97.57(3)
g (◦ ) 90.00 90.00 90.00 81.53(1) 79.16(3) 99.11(3) 76.62(1) 90.00 90.00
T/K 100 100 173 100 100 100 100 100 100
V /Å3 2991.1(6) 2165.9(2) 2377.8(2) 2030.2(1) 2493.7(9) 1814.0(6) 1958.9(5) 4404.5(2) 5418.7(19)
Z 4 4 4 2 2 2 2 4 4
m/mm-1 0.919 0.905 0.924 0.866 0.819 0.888 0.760 0.805 0.908
Reflections 21548 59330 12253 45489 28328 20298 22642 52164 49779
collected
Independent 6839 (0.0313) 7787 (0.0927) 5463 (0.0373) 10904 (0.0476) 11391 (0.0289) 8295 (0.1923) 8958 (0.0441) 12074 (0.0548) 11043 (0.0991)
reflections (Rint )
Final R indices 0.0325, 0.0966 0.0491, 0.1185 0.0312, 0.0720 0.0351, 0.0816 0.0363, 0.0871 0.0482, 0.1057 0.0412, 0.1122 0.0392, 0.0936 0.0640, 0.1737
[I2s(I)]: R1,wR2

Dalton Trans., 2010, 39, 11616–11627 | 11625

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Experimental
The preparation, purification and reactions of the complexes de-
scribed were carried out using standard Schlenk techniques under
an atmosphere of dry nitrogen; solvents were dried using Anhy-
drous Engineering double alumina or alumina/copper catalyst
columns and deoxygenated prior to use. The compounds Htaz,3
KTp, KTpMe2 , KTpPh ,17 [{Rh(cod)(m-Cl)}2 ]18 and [{Rh(nbd)(m-
Cl)}2 ]19 were prepared by published methods.
Solution IR spectra were recorded on a PerkinElmer Spectrum
One FT-IR spectrometer over the range 2200-1600 cm-1 , in CH2 Cl2
using CaF2 cells with a 1 mm path length. NMR spectra were
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A
recorded on a JEOL Eclipse 300 spectrometer, operating at
299.9 MHz for 1 H, at 75.4 MHz for 13 C, at 96.2 MHz for 11 B
and at 121.4 MHz for 31 P, using JEOL Delta software. For 1 H and
13
C-{1 H} spectra, either SiMe4 or residual protio solvent was used
as an internal standard. For 31 P-{1 H} spectra, 85% H3 PO4 was
used as an external standard. For 11 B-{1 H} spectra, BF3 ·OEt2 was
Downloaded by Bristol University on 05 March 2011
used as an external standard. Microanalyses were carried out by
the staff of the Microanalytical Service of the School of Chemistry,
University of Bristol.
Syntheses
K[HB(taz)2 (pzMe2 )] K+ 2- . A mixture of Htaz (4.52 g,
31.6 mmol) and KTpMe2 (5.31 g, 15.8 mmol) was ground together
and then sealed in a Schlenk tube under a static vacuum. The
lower portion of the tube was heated to 125 ◦ C for ca. 90
min, during which time colourless crystals of HpzMe2 sublimed
onto the upper portions of the vessel. The solid mass left at
the bottom of the Schlenk tube was cooled and thf (50 cm3 )
added. Vigorous agitatation/sonication gave a suspension of the
white solid product which was collected by filtration, washed with
further thf and dried in vacuo, yield 5.26 g (77%).
The salts K[HB(taz)2 (pz)] K+ 1- , K[HB(taz)2 (pzPh )] K+ 3- and
K[HB(pz)2 (taz)] K+ 4- were prepared by modifications of this
method from KTpR and suitable proportions of Htaz, at 130,
150 and 100 ◦ C respectively; the solid products were washed with
CH2 Cl2 . The reaction time for K+ 1- and K+ 4- was reduced to 60
min.
[Rh(cod){HB(taz)2 (pzMe2 )}] 6. Solid K+ 2- (1.31 g, 3.04 mmol)
was added to a yellow solution of [{Rh(cod)(m-Cl)}2 ] (733 mg,
1.49 mmol) in CH2 Cl2 (60 cm3 ). The mixture was stirred for 1.5 h
at room temperature and then filtered, giving a red-orange solution
which was concentrated in vacuo to ca. 5 cm3 . n-Hexane was
then added to precipitate the crude solid which was subsequently
purified using CH2 Cl2 –n-hexane to give a yellow-orange solid,
yield 1.45 g (81%).
The complexes [Rh(cod){HB(taz)2 (pz)}] 5, [Rh(cod){HB-
(taz)2 (pzPh )}] 7 and [Rh(cod){HB(taz)(pz)2 }] 8 were prepared
similarly using the appropriate potassium scorpionate salt.
[Rh(CO)(PPh3 ){HB(taz)2 (pzMe2 )}] 19. Carbon monoxide was
bubbled through 6 (162 mg, 269 mmol) in CH2 Cl2 (50 cm3 ) for
15 min. Solid PPh3 (75 mg, 278 mmol) was then added and the
mixture stirred for a further 60 min. Addition of n-hexane and
concentration of the mixture in vacuo gave a yellow-orange solid
which was then purified using CH2 Cl2 –n-hexane to give a yellow
solid, yield 134 mg (64%).
11626 | Dalton Trans., 2010, 39, 11616–11627
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The complexes [Rh(CO)(PPh3 ){HB(taz)(pz)2 }] 12, [Rh(CO)-
(PPh3 ){HB(taz)2 (pz)}] 16, [Rh(CO)(PCy3 ){HB(taz)2 (pzMe2 )}]
17, [Rh(CO){P(NMe2 )3 }{HB(taz)2 (pzMe2 )}] 18 and [Rh(CO)-
{P(OPh)3 }{HB(taz)2 (pzMe2 )] 20 and [Rh(CO)(PPh3 ){HB-
(taz)2 (pzPh )}] 21 were prepared similarly from the appropriate
rhodium scorpionate complex and tertiary phosphine.
[Rh{B(taz)2 (pzMe2 )}{HB(taz)2 (pzMe2 )}] 23. Solid K+ 2-
(500 mg, 1.16 mmol) was added to an orange solution of
[{Rh(nbd)(m-Cl)}2 ] (268 mg, 581 mmol) in CH2 Cl2 (60 cm3 ). The
mixture, initially green and then, after 45 min, yellow-brown, was
filtered to give an orange solution which was concentrated in
vacuo to ca. 5 cm3 . The concentrate was loaded onto an activated
alumina (grade III)/CH2 Cl2 chromatography column from which
an orange band was eluted using CH2 Cl2 :thf (1 : 1). The orange
eluate was concentrated to a minimum volume in vacuo. n-Hexane
was then added to precipitate the product as an orange solid,
yield 69 mg (13%).
Structure determinations of complexes 6, 8, 10, 16–19, 21 and 23
Many of the details of the structure analyses of
[Rh(cod)L] {Tx = HB(taz)2 (pzMe2 ) 6, HB(taz)(pz)2 8},
[Rh(CO)2 {HB(taz)2 (pzMe2 )}] 10, [Rh(CO)(PPh3 ){HB(taz)2 (pz)}]
16, [Rh(CO)(PR3 ){HB(taz)2 (pzMe2 )}] (R = Cy 17, NMe2 18,
Ph 19), [Rh(CO)(PPh3 ){HB(taz)2 (pzPh )}] 21 and [Rh{B(taz)2 -
(pzMe2 )}{HB(taz)2 (pzMe2 )}] 23 are listed in Table 8.
X-ray diffraction experiments on 10 and 23 were carried out
at 173 K on a Bruker SMART diffractometer; experiments on
6, 17, 18 and 19 were carried out at 100 K on a Bruker APEX
II diffractometer; experiments on 8, 16 and 21 were carried out
at 100 K on an Oxford Diffraction Gemini diffractometer. Data
were collected using Mo-Ka radiation (l = 0.71073 Å) using
a CCD area detector on a single crystal mounted on a glass
fibre. Intensities were integrated20 from several series of exposures
measuring 0.5◦ or 0.3◦ in w or j. Absorption corrections were
based on equivalent reflections using SADABS21 or CrysAlis
RED.22 Structures were solved using ShelXS and refined against
all Fo 2 data using SHELXL.23 The positions of all hydrogen atoms
were calculated and refined using a riding model, including those
on boron.
Acknowledgements
We thank the EPSRC for postgraduate studentships (to R.J.B.
and A.H.), Johnson Matthey for a generous loan of hydrated
rhodium trichloride, and Oxford Diffraction for the loan of a
diffractometer. We acknowledge the use of the EPSRC’s Chemical
Database Service at Daresbury.24
Notes and references
1 S. Trofimenko, Scorpionates; The Coordination Chemistry of Polypyra-
zolylborate Ligands, Imperial College Press, London, 1999.
2 M. D. Spicer and J. Reglinski, Eur. J. Inorg. Chem., 2009, 1553.
3 M. Careri, L. Elviri, M. Lanfranchi, L. Marchiò, C. Mora and M. A.
Pellinghelli, Inorg. Chem., 2003, 42, 2109.
4 B. Benkmil, M. Ji and H. Vahrenkamp, Inorg. Chem., 2004, 43, 8212;
M. Ji, B. Benkmil and H. Vahrenkamp, Inorg. Chem., 2005, 44, 3518.
5 C. Kimblin, T. Hascall and G. Parkin, Inorg. Chem., 1997, 36, 5680; C.
Kimblin, B. M. Bridgewater, D. G. Churchill, T. Hascall and G. Parkin,
Inorg. Chem., 2000, 39, 4240.
This journal is © The Royal Society of Chemistry 2010

6 M. Shu, R. Walz, B. Wu, J. Seebacher and H. Vahrenkamp, Eur. J.
Inorg. Chem., 2003, 2502.
7 I. R. Crossley, Adv. Organomet. Chem., 2008, 56, 199.
8 N. G. Connelly, D. J. H. Emslie, W. E. Geiger, O. D. Hayward, E. B.
Linehan, A. G. Orpen, M. J. Quayle and P. H. Rieger, J. Chem. Soc.,
Dalton Trans., 2001, 670; N. G. Connelly, D. J. H. Emslie, B. Metz, A.
G. Orpen and M. J. Quayle, Chem. Commun., 1996, 2289.
9 M. J. López-Gómez, N. G. Connelly, M. F. Haddow, A. Hamilton and
A. G. Orpen, Dalton Trans., 2010, 39, 5221.
10 R. J. Blagg, C. J. Adams, J. P. H. Charmant, N. G. Connelly, M. F.
Haddow, A. Hamilton, J. Knight, A. G. Orpen and B. M. Ridgway,
Dalton Trans., 2009, 8724; R. J. Blagg, J. P. H. Charmant, N. G.
Connelly, M. F. Haddow and A. G. Orpen, Chem. Commun., 2006,
2350.
11 I. R. Crossley, A. F. Hill and A. C. Willis, Organometallics, 2006, 25,
Published on 01 November 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00774A
289.
12 V. K. Landry, J. G. Melnick, D. Buccella, K. Pang, J. C. Ulichny and
G. Parkin, Inorg. Chem., 2006, 45, 2588.
13 C. E. Webster and M. B. Hall, Inorg. Chim. Acta, 2002, 330, 268.
Downloaded by Bristol University on 05 March 2011
This journal is © The Royal Society of Chemistry 2010
View Online
14 M. Akita, K. Ohta, Yo. Takahashi, S. Hikichi and Yo. Moro-oka,
Organometallics, 1997, 16, 4121.
15 C. J. Adams, K. M. Anderson, J. P. H. Charmant, N. G. Connelly, B.
A. Field, A. J. Hallett and M. Horne, Dalton Trans., 2008, 2680.
16 C. A. Tolman, Chem. Rev., 1977, 77, 313.
17 S. Trofimenko, Inorg. Synth., 1970, 12, 99.
18 G. Giordano and R. H. Crabtree, Inorg. Synth., 1990, 28, 88.
19 E. W. Abel, M. A. Bennett and G. Wilkinson, J. Chem. Soc., 1959, 3178.
20 For complexes 6, 10, 18 and 19: Bruker-AXS SAINT V6.41, Bruker,
2002; for complex 17: SAINT V7.68A, Bruker, 2010; for complexes 8,
16, 21, 23: CrysAlis RED V1.171.32.5, Oxford Diffraction Ltd., 2007.
21 G.M. Sheldrick, SADABS V2008/1 (complex 17), V2.03 (complexes
10 and 18) or V2.10 (complexes 6 and 19), University of Göttingen,
Germany.
22 CrysAlis RED, V1.171.32.5, Oxford Diffraction Ltd, 2007 (complexes
8, 16, 21 and 23.
23 G. M. Sheldrick, Acta Cryst., 2008, A64, 112.
24 D. A. Fletcher, R. F. McMeeking and D. Parkin, J. Chem. Inf. Comput.
Sci., 1996, 36, 746.
Dalton Trans., 2010, 39, 11616–11627 | 11627