(Diphenylphosphino)alkyl-functionalized nucleophilic carbene complexes of palladium

Tsoureas, Nikolaos, Danopoulos, Andreas A, Tulloch, Arran A D and Light, Mark E (2003) (Diphenylphosphino)alkyl-functionalized nucleophilic carbene complexes of palladium. Organometallics, 22 (23). pp. 4750-4758. ISSN 0276-7333

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Abstract

The (diphenylphosphino)alkyl-functionalized nucleophilic heterocyclic carbene (NHC) complexes of palladium LPdX2 (L = (3-R1)[1-Ph2P(CH2)2]-imidazol-2-ylid ene; R1 = 2,6-Pr2iC6H3, 2,4,6-Me3C6H2; X = CH3 (3a,b), X = Br (4a,b)) have been synthesized by the reaction of the in situ generated functionalized NHC ligand La or Lb with Pd(tmed)(CH3)2 and Pd(COD)Br2, respectively, and structurally characterized. Interaction of 3a with H(Et2O)- {B[3,5-(CF3)2C6H2]4} and pyridine or with (CF3)2CHOH and pyridine in CH2Cl2 gave the monocationic complexes [(La)Pd(CH3)(pyridine)]+(A)- (A- = {B[(3,5-CF3)2C6H2]4} -, (CF3)2CHO-); acetonitrile and benzonitrile analogues can be prepared in an analogous way. Reaction of 4a with AgBF4 in MeCN gave the dicationic complexes [(La)Pd(MeCN)2](BF4)2. Complexes 3 show moderate catalytic activity for the coupling of acrylates with aryl bromides but not chlorides. The cationic species generated in situ from 3a and H(Et2O){B[(3,5-CF3) 2C6H2]4} in CH2Cl2 under CO/ethylene acts as a copolymerization catalyst under mild conditions.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
SWORD Depositor: Mx Elements Account
Depositing User: Mx Elements Account
Date Deposited: 01 Nov 2021 10:00
Last Modified: 01 Nov 2021 10:00
URI: http://sro.sussex.ac.uk/id/eprint/102583

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