173986-44-2Relevant articles and documents
Synthesis of Methyl-palladium(II) and -platinum(II) Complexes containing Labile Chelates and Olefinic Tertiary Phosphine Ligands: Intramolecular Insertion of an Olefin into a Palladium-Carbon Bond, and Activation of a Carbon-Hydrogen Bond by a Platinum(II) Complex
Cavell, Kingsley J.,Jin, Hong
, p. 4081 - 4090 (2007/10/02)
The square planar complexes (M = Pd, L = dpvp , L-L = acac (acetylacetonate), bzsac (1-phenyl-3-sulfanylbut-2-en-1-onate) or pyca (pyridine-2-carboxylate), L = PPh2(C6H4Et-o), L-L = acac or pyca, L = P(CH2-CH=CH2)Ph2, L-L = pyca; M = Pt, L = dpvp, L-L = bzsac or pyca, L = PPh2(C6H4Et-o), L-L = pyca) have been synthesised and their thermal behaviour studied.Heating the palladium-dpvp complexes in benzene leads to intramolecular migratory insertion of the vinyl double bond of the phosphine into the Pd-Me bond to give complexes with a five-membered palladacyclic ring, .In contrast, warming the platinum complex leads to a cyclometallation reaction forming a platinacycle with a platinum-alkenyl bond .The platinum complex appears to react by oxidative addition of the vinyl C-H bond of dpvp to PtII; methane is eliminated during the reaction.Although no such species has been identified, kinetic evidence suggests that the two thermal processes occur via a common four-co-ordinate intermediate containing a 'dangling' pyca ligand and with dpvp chelated through the phosphorus and the vinyl double bond .
