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Synthesis and reaction chemistry of mixed ligand methylpalladium-carbene complexes
Citation
McGuinness, DS and Green, MJ and Cavell, KJ and Skelton, BW and White, AH, Synthesis and reaction chemistry of mixed ligand methylpalladium-carbene complexes, Journal of Organometallic Chemistry, 565, (1-2) pp. 165-178. ISSN 0022-328X (1998) [Refereed Article]
DOI: doi:10.1016/S0022-328X(98)00455-0
Abstract
A variety of methylpalladium carbene complexes of the type [Pd(Me)(carbene)(chelate)] [where carbene=1,3-di-methylimidazol-2-ylidene (dmiy), chelate=acetylacetonate (acac) 1, trifluoroacetylacetonate (tfac) 2, hexafluoroacetylacetonate (hfac) 3; carbene=1,3,4,5-tetramethylimidazol-2-ylidene (tmiy), chelate=acac, 6] have been synthesised and fully characterised. The bis-carbene complexes trans-[Pd(Me)(carbene)2Cl] [carbene=dmiy, 7 and tmiy, 8] have also been isolated. The unusual cationic complex {[Pd(Me)(dmiy)(cod)]+BF4 -} 4, in which there are three distinct Pd-carbon bonds, including cis alkyl/alkene coordination has been prepared and aspects of its chemistry investigated. The complex which slowly decomposes even at -20°C does not react via the expected migratory insertion of the methyl group with the coordinated cod but decomposes via a pathway involving the methyl group and the carbene ligand. Crystal structures of the bis-carbene complex 7 and the chloro-bridged dimer [Pd(Me)(tmiy)Cl]2 5 reveal square planar coordination. The carbene C3N2 arrays are closely planar, with the ligand planes inclined at significant angles to the coordination planes of the respective complexes. For complex 7 the interplanar dihedral angle is 70.4(3)° and for 5 the angle is 65.07(8)°. Examples of the methylpalladium monocarbene and dicarbene complexes were tested in the Heck reaction and were found to be extremely active with several having turnover frequencies (TOF's) of >20 000 and total turnover numbers (TON's) of >100 000.
Item Details
| Item Type: | Refereed Article |
|---|---|
| Research Division: | Chemical Sciences |
| Research Group: | Inorganic chemistry |
| Research Field: | Transition metal chemistry |
| Objective Division: | Expanding Knowledge |
| Objective Group: | Expanding knowledge |
| Objective Field: | Expanding knowledge in the chemical sciences |
| UTAS Author: | McGuinness, DS (Dr David McGuinness) |
| UTAS Author: | Green, MJ (Ms Melinda Jane Green) |
| UTAS Author: | Cavell, KJ (Professor Kingsley Cavell) |
| ID Code: | 14125 |
| Year Published: | 1998 |
| Web of Science® Times Cited: | 218 |
| Deposited By: | Chemistry |
| Deposited On: | 1998-08-01 |
| Last Modified: | 2011-08-09 |
| Downloads: | 0 |
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