646068-12-4Relevant articles and documents
Reaction of Palladium and Platinum Complexes Bearing α,/β-Unsaturated Carbonyl Compounds with Carbon Electrophiles: Control over Site of Electrophilic Attack, Oxygen or Metal
Morita, Masaki,Inoue, Katsuharu,Ogoshi, Sensuke,Kurosawa, Hideo
, p. 5468 - 5472 (2008/10/09)
The reaction of (η2-CH2=CHCHO)ML2 (M = Pd, Pt; L = PPh3, L2 = DPPF) with methyl triflate gave η3-methoxyallyl complexes [(η3-CH 3OCHCHCH2)ML2][OTf]. X-ray diffraction analysis on [(η3-CH3OCHCHCH2)M(dppf)] [OTf] (M = Pd, Pt) showed a distorted η3-allyl structure. The enone complexes (η2-CH2=CHCOCH3)M(PPh 3)2 also reacted with methyl triflate to give [(η 3-CH3OC(CH3)CHCH2)M(PPh 3)2] [OTf]. It was proposed that these complexes were formed by the direct electrophilic attack of methyl triflate at the carbonyl oxygen of the enal or enone ligand on the palladium and platinum. In fact, no insertion of acrolein into the platinum-methyl bond of the separately isolated methylplatinum complex proceeded. On the other hand, methyl iodide underwent oxidative addition with zerovalent enal or enone complexes to give methylmetal complexes concomitant with dissociation of an enal or enone molecule.