Transition Metal Complexes on N-Heterocyclic carbenes Soh W. C. + and Huynh H. V.

*
Department of Chemistry, Faculty of Science, National University of Singapore 3 Science Drive 3, Singapore 117543 ABSTRACT The carbene precursor 1,3-diisopropylbenzimidazolium bromide (iPr2-bimyH+Br-) (A) has been prepared with reference to literature[1]. Reaction of A with Pd(OAc)2 and NaBr gave the dimeric Pd(II) benzimidazolin-2-ylidene complex [PdBr2(iPr2-bimy)]2 (1)[1]. The dimer is subsequently reacted with an N-heterocyclic ligand to afford the benzannulated monocarbene complexes trans-[PdBr2(L)(iPr2-bimy)] (2) X-ray diffraction studies on single crystals of 2(ah) revealed a square planar geometry with orientation of the N-isopropyl substituents with the C-H group pointing to the metal center, suggest interaction of C-HPd[1]. The large downfield shift of the C-H protons in the 1H NMR spectrum compared to the precursor A[1] indicates that these C-HPd interactions are retained in solution and can be described as weak agnostic interactions. The strength of these C-HPd interactions is investigated by substitution of different heterocyclic ligands to form 2(a-h). The C-H chemical shift of the isopropyl groups are noted and compared with crystal data to investigate if the strength of anagostic interaction could be determined by NMR spectroscopy. Introduction N-heterocyclic carbenes (NHC) and their respective transition metal complexes have been the focus of organometallic chemistry research for the past decade[2]. In this project, isolation and characterization of trans-[PdBr2(L)(iPr2-bimy)] carbene complexes is reported. These complexes exhibit unusual C-HPd interactions, also known as anagostic interactions. Anagostic interactions refer to Pd H bond distance of 2.3A to 2.9A with C-H-M angle of 110 to 170 with downfield shift of the C-H-M in particular.[3] Anagostic interactions are essentially different from hydrogen bonds. In the case of anagostic interactions, the hydrogen supplies electrons to the metal atom, whereas in hydrogen bonds, the hydrogen seeks electron from the corresponding bonding atom. In simpler terms, anagostic and agnostic interactions describe a two electron 3 center bonding interaction and hydrogen bonding describes a four electron 3 center interaction.[4]. Previously, it has been reported that precursor salt A has chemical shift of isopropyl groups at 5.21ppm; Complex 1 with its corresponding signal at 6.54ppm and complex 3, the dicarbene complex with corresponding signal at 6.25ppm.[5] By comparing the downfield shift of isopropyl group of salt A and the rest of the complexes, it is suspected that anagostic interaction exist at the isopropyl protons to the metal center.[1] As such, it is of interest to find out if the addition of different N-heterocycles would affect the anagostic interactions and if the results could be characterized accordingly.

N N

Br Pd Br 3

N N

Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)

Results and discussion Palladium(II) dimer 1 was synthesized in accordance to literature methods[1] (Scheme 1) at high yields of 88%. In general, the synthesis of benzannulated monocarbene complexes trans[PdBr2(L)(iPr2-bimy)] can be conveniently prepared by stirring 1 with the targeted Nheterocycle with 2:1 ratio, at ambient temperature (Scheme 2). Complexes 2(a-h) (Diagram 1) were synthesized, successfully obtaining pure crystals.
N 4eq KBr + Pd(OAc)2 N A Scheme 1 DMSO, 90 , 24h
o

N Br

N Br

Br Pd Br Pd

Br N N

Diagram 1

2a

2b

2c

2d

2e

2f

2g

2h

2i was found to undergo isomerisation to cis complex, 2i* when its solution in deuterated chloroform was left to stand for days (Diagram 2). NMR studies in deuterated chloroform showed an increase in corresponding cis-complex signals. Formation of cis complex was proven via the difference in 3J(H-H) coupling of the methyl groups (doublet). For trans benzannulated mono-carbene complexes, it was noted that the doublet has coupling constant of 7.08Hz. When solution was left to stand, new doublets were observed, with coupling constant of 6.9Hz. The rate of isomerisation could not be determined due to the close proximity and overlapping of the signals. A similar trend was noticed for 2j, with 1-methylbenzimidazole as the ligand (Diagram 3). An attempt was made to synthesize similar complexes with triazole based ligands, However, there were complications due to possibilities of isomerisation and dimerization

N N

Br Pd N Br

L-1-methylbenzimidazole

2i

2i*

2j

2j*

Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)

Diagram 2 Diagram 3 From Table 2, we can observe that the larger the M-H-C angle, the smaller the bond Pd-H bond distance. This may be an indication that the isopropyl proton is bent slightly towards the metal centre, thus there exist an anagostic interaction between the proton and the metal centre. The more the bending of the isopropyl proton, the larger the M-H-C angle, and thus a stronger interaction, indicated by the bond distance. Table 2: Bond length and bond angles of C-HPd interaction Complex 2a 2b 2c 2d 2e 2f 2g 2h M---H-C Bond Length1 () 2.662 2.748 2.762 2.790 2.768 2.748 2.749 2.826 M---H-C Angle1 120.9 120.24 120.03 119.64 119.75 120.25 120.22 118.92 M---H-C Bond Length2 () 2.604 2.696 2.651 2.640 2.638 2.699 2.643 2.666 M---H-C Angle2 129.03 121.53 121.42 121.54 121.01 121.33 121.68 120.54

Table 3: Chemical shift of isopropyl proton and Ccarbene Average Bond length () 2.633 2.722 2.707 2.715 2.703 2.724 2.696 2.746 (ppm) C-H 6.30 6.33 6.33 6.33 6.35 6.38 6.42 6.47 6.48 6.51 (ppm) Carbene 158.5 162.9 160.4 161.4 160.9 160.9 159.7 159.7 Pd-Ccarbene bond distance 1.964 1.952 1.945 1.943 1.955 1.949 1.953 1.948

Complex 2f 2d 2g 2e 2h 2c 2a 2b 2j 2i

From Table 3, the insignificant change of isopropyl proton chemical shift would probably be due to the similar electronic properties of these ligands with slight differences of electronegativity on the coordinating N atom. Comparing 2i, 2j, 2b and 2a, the difference would be a NH, NCH3, S and O atom respectively. Whereas, a comparison of the electronegativity of these 3 complexes would probably be ranked as NCH3 < NH < S < O. Comparing 2c, 2d and 2e the electron density at N coordinating atom would probably be ranked as 2d > 2c > 2e. However, with decreasing electron density at N coordinating atom, there is a slight decrease in Pd-Ccarbene distance. In comparison of the 1H NMR of the isopropyl signals, 13C NMR of the Ccarbene signal, average bond distance of the Pd-Ccarbene and C-HPd distance, no direct relation could be observed.

Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)

Following Scheme 5, an attempt was made to catalyze this BuchwaldHartwig Amination reaction following literature methods [10]. However, product 4 was not observed to have formed in this reaction. Change of base did not improve the reaction. More investigation has to be done in order to determine the suitability of 2a as a catalyst Conclusion The use of different N-heterocycles to cleave dimer 1 formed complexes with significant anagostic interactions. The strength of the Pd-carbene bond is affected by the electronic properties of the corresponding ligand used to cleave the dimer 1. The use of different ligands has also affected the anagostic C-HPd bond distance. However, the anagostic interaction could not be characterized by 1H NMR or 13C NMR. In addition, due to sensitivity of equipment, the bond distance of anagostic interaction could not be determined exactly. However, the bond distances serve as an indication of the anagostic interactions. Acknowledgements I would like to thank my supervisor, Dr Huynh for his sound advices; PhD and honors students under Dr Huynhs group, especially Han Yuan and Wu jiang; staffs of Department of Chemistry (NUS) and lastly, friends who have offered their assistance in one way or another. References: 1. Han Vinh Huynh, Yuan Han, Joanne Hui Hui Ho, Geok Kheng Tan, Organometallics 2006, 25,3267-3274 2. (a) Herrmann, W. A.; Kocher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2162. (b) Tamm, M.; Hahn, F. E. Coord. Chem. ReV. 1999, 182, 175. (c) Bourissou, D.; Guerret, O.; Gabba, F. P.; Bertrand, G. Chem. ReV. 2000, 100, 39. (d) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290. (e) Hillier, A. C.; Grasa, G. A.; Viciu, M. S.; Lee, H. M.; Yang, C.; Nolan, S. P. J. Organomet. Chem. 2002, 653, 69. (f) Cavell, K. J.; McGuinness, D. S. Coord. Chem. ReV. 2004, 248, 671. (g) Cesar, V.; BelleminLapnnaz, S.; Gade, L. H. Chem. Soc. ReV. 2004, 33, 619. (h) Hahn, F. E. Angew. Chem., Int. Ed. 2006, 45, 1348 3. Maurice Brookhart, Malcolm L. H. Green, and Gerard Parkin, PNAS 24 Apr 2007, 104 , 17, 69086914 4. F. Albert Cotton, Geoffrey Wilkinson, Carlos A. Murillo and Manfred Bochman, Advanced Inorganic Chemistry, Sixth Edition, 89-90 5. Y. Han et al. J. Organometallic Chemistry 2007, 692, 36063613 6. (a) M.J. Bhanushali et al. Journal of Molecular Catalysis A 2006 Chemical 259 4650 (b) Michael S. Driver and John F. Hartwig, J. Am. Chem. Soc. 1996, 118, 7217-7218 (c) S. L. Parisel et al., Tetrahedron 2005, 61, 98229826 (d) L. Djako6itch et al., J. Organometallic Chemistry 1999, 592, 225234

Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)