(1)Pyridine and phosphine functionalised N-heterocyclic carbene complexes of rhodium and iridium
(1)Pyridine and phosphine functionalised N-heterocyclic carbene complexes of rhodium and iridium
The pyridine functionalised N-heterocyclic carbene complexes [M(kappa(2)-NCDIPP)(COD)](+)A(-), NCDIPP = 3-(2, 6-(Pr2C6H3)-C-i)-1-[2-(3-picolyl)]-imidazol-2-ylideni, A(-) = [(Ar4B)-B-F](-), [{3,5-(CF3)(2)C6H2}(4)B](-), M = Rh, 1b, Ir, 4, have been prepared in two steps by reaction of the [M(COD)Cl](2) with the isolated NCDIPP to [Rh(kappa(1)-NCDIPP)(COD)Cl], 2, and [Ir(kappa(2)-NCDIPP)(COD)Cl], 3, followed by anion exchange with Na(+)A(-). The phosphine functionalised N-heterocyclic carbene complex [Rh(PCH2Cmes)(2)]Br, 6, PCH2Cmes = 1-(diphenylphosphino-methyl)-3-(2,4,6-Me3C6H2)-imidazol-2-ylidene, was prepared by the reaction of the [Rh(COD)Cl](2) with the corresponding N-heterocyclic carbene generated in situ. Monomeric [Rh(PCH2CH2CDIPP)(acac)], 7 was prepared by an analogous reactions from [Rh(COE)(2)(acac)]. In contrast, phosphine functionalised N-heterocyclic carbene complexes of iridium (I) were not easily accessible. However, the reaction of [Ir(COD)(mu-Cl)2(mu-H)]2 with PCH2CH2Cmes gave complex [Ir(COD)(PCH2CH2Cmes.)Br], 8, in which the carbene is coordinated to the metal in an 'abnormal' mode.
arduengo carbene, iridium, rhodium, functionalised heterocyclic
carbene, pyridine, crystal structure
transfer hydrogenation, imidazolium salts, ligand-binding, catalysts, irh5(pph3)(2), activation, palladium, chelate, bearing, ketones
5948-5958
Stylianides, Neoklis
3fe7867a-206a-4740-9d78-3a36d5155c38
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
2005
Stylianides, Neoklis
3fe7867a-206a-4740-9d78-3a36d5155c38
Danopoulos, Andreas A.
4919c13e-ebe4-4456-b329-c806c8e22236
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Stylianides, Neoklis, Danopoulos, Andreas A. and Tsoureas, Nikolaos
(2005)
(1)Pyridine and phosphine functionalised N-heterocyclic carbene complexes of rhodium and iridium.
Journal of Organometallic Chemistry, 690 (24-25), .
(doi:10.1016/j.jorganchem.2005.07.094).
Abstract
The pyridine functionalised N-heterocyclic carbene complexes [M(kappa(2)-NCDIPP)(COD)](+)A(-), NCDIPP = 3-(2, 6-(Pr2C6H3)-C-i)-1-[2-(3-picolyl)]-imidazol-2-ylideni, A(-) = [(Ar4B)-B-F](-), [{3,5-(CF3)(2)C6H2}(4)B](-), M = Rh, 1b, Ir, 4, have been prepared in two steps by reaction of the [M(COD)Cl](2) with the isolated NCDIPP to [Rh(kappa(1)-NCDIPP)(COD)Cl], 2, and [Ir(kappa(2)-NCDIPP)(COD)Cl], 3, followed by anion exchange with Na(+)A(-). The phosphine functionalised N-heterocyclic carbene complex [Rh(PCH2Cmes)(2)]Br, 6, PCH2Cmes = 1-(diphenylphosphino-methyl)-3-(2,4,6-Me3C6H2)-imidazol-2-ylidene, was prepared by the reaction of the [Rh(COD)Cl](2) with the corresponding N-heterocyclic carbene generated in situ. Monomeric [Rh(PCH2CH2CDIPP)(acac)], 7 was prepared by an analogous reactions from [Rh(COE)(2)(acac)]. In contrast, phosphine functionalised N-heterocyclic carbene complexes of iridium (I) were not easily accessible. However, the reaction of [Ir(COD)(mu-Cl)2(mu-H)]2 with PCH2CH2Cmes gave complex [Ir(COD)(PCH2CH2Cmes.)Br], 8, in which the carbene is coordinated to the metal in an 'abnormal' mode.
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Published date: 2005
Additional Information:
Carbene chemistry
Keywords:
arduengo carbene, iridium, rhodium, functionalised heterocyclic
carbene, pyridine, crystal structure
transfer hydrogenation, imidazolium salts, ligand-binding, catalysts, irh5(pph3)(2), activation, palladium, chelate, bearing, ketones
Identifiers
Local EPrints ID: 44551
URI: http://eprints.soton.ac.uk/id/eprint/44551
ISSN: 0022-328X
PURE UUID: a2a615e3-759a-4c5b-8902-7e918d375cd8
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Date deposited: 02 Mar 2007
Last modified: 15 Mar 2024 09:05
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Author:
Neoklis Stylianides
Author:
Andreas A. Danopoulos
Author:
Nikolaos Tsoureas
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