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Synthesis of N-heterocyclic carbene palladium(II) bis-phosphine complexes and their decomposition in the presence of aryl halides

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Magill, AM and Yates, BF and Cavell, KJ and Skelton, BW and White, AH (2007) Synthesis of N-heterocyclic carbene palladium(II) bis-phosphine complexes and their decomposition in the presence of aryl halides. Dalton Transactions (31). pp. 3398-2406. ISSN 1477-9226

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Abstract

Methylpalladium(II) carbene complexes of the type [Pd(NHC)Me(P–P)]BF4 (NHC = N-heterocyclic
carbene, P–P = chelating phosphine) have been synthesised, the complex [Pd(tmiy)Me(dcype)]BF4
(tmiy = 1,3,4,5-tetramethylimidazol-2-ylidene, dcype = 1,2-bis(dicyclohexylphosphino)ethane) being
characterised crystallographically. Complexes bearing the tmiy ligands were shown to decompose in an
analogous manner to complexes bearing monodentate phosphine ligands, with the rate of
decomposition being nominally linked to the size of the chelate ring. The decomposition of these
complexes in the presence of aryl halides—expected to yield Pd(Ar)X(P–P)—was studied and shown
instead to yield PdX2(P–P) and [Pd(tmiy)X(P–P)]BF4. Additionally, Pd(Me)X(P–P) and Pd(Ar)X(P–P)
were observed in some cases. Intermolecular cross-over reactions between the starting complex and
Pd(Ar)X(P–P) were found to be the source of these unexpected products.

Item Type: Article
Journal or Publication Title: Dalton Transactions
Publisher: Royal Society of Chemistry
Page Range: pp. 3398-2406
ISSN: 1477-9226
Identification Number - DOI: 10.1039/b706053j
Additional Information:

Copyright © 2007 Royal Society of Chemistry

Date Deposited: 07 Apr 2008 14:41
Last Modified: 18 Nov 2014 03:35
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