title: Synthesis of N-heterocyclic carbene palladium(II) bis-phosphine complexes and their decomposition in the presence of aryl halides creator: Magill, AM creator: Yates, BF creator: Cavell, KJ creator: Skelton, BW creator: White, AH subject: 259901 Organometallic Chemistry description: 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. publisher: Royal Society of Chemistry date: 2007 type: Article type: PeerReviewed format: application/pdf identifier: http://eprints.utas.edu.au/4468/1/4468.pdf relation: http://dx.doi.org/10.1039/b706053j identifier: 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 relation: http://eprints.utas.edu.au/4468/