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Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands


Reference:

Douglas, S., Lowe, J. P., Mahon, M. F., Warren, J. E. and Whittlesey, M. K., 2005. Synthesis and structural characterisation of rhodium hydride complexes bearing N-heterocyclic carbene ligands. Journal of Organometallic Chemistry, 690 (23), pp. 5027-5035.

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Abstract

Addn. of excesses of N-heterocyclic carbenes (NHCs) IEt2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixt. of [HRh(NHC)(PPh3)2] [NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4)] and [HRh(NHC)2(PPh3)] [NHC = IEt2Me2(cis-/trans-5), IiPr2Me2 (cis-/trans-6), ICy (cis-/trans-7)]. Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH2), affords the bridging hydrido phosphido dimer, [{(PPh3)2Rh}2(micro -H)(micro -PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the Rh precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(IiPr2Me2)2] (cis-/trans-12) and the unusual unsym. dimer, [(PPh3)2Rh(micro -CO)2Rh(IiPr2Me2)2] (13). Trans-3, 8, 10 and 13 were structurally characterized.

Details

Item Type Articles
CreatorsDouglas, S., Lowe, J. P., Mahon, M. F., Warren, J. E. and Whittlesey, M. K.
Uncontrolled Keywordsmolecular structure (of rhodium hydride complexes with n-heterocyclic carbene imidazolylidene ligands), diastereomers (geometric, mol structure rhodium hydride heterocyclic carbene imidazolylidene ligand, prep (preparation) (prepn. and structure of rhodium hydride complexes with n-heterocyclic carbene imidazolylidene ligands), prp (properties), rct (reactant), rhodium hydride heterocyclic carbene imidazolylidene ligand prepn structure, crystal structure rhodium hydride heterocyclic carbene imidazolylidene ligand prepn, ract (reactant or reagent) (nitrogen, prepn. and structure of rhodium hydride complexes with n-heterocyclic carbene imidazolylidene ligands), five-membered-ring, crystal structure, heterocyclic compounds role, carbene complexes role, spn (synthetic preparation)
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4825

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