116563-66-7Relevant articles and documents
Intermolecular activation of C-D bonds in benzene-d6 by trans-neopentyl(trifluoromethanesulfonato)bis(trimethyl-phosphine) platinum (II)
Brainard, Robert L.,Rodger Nutt,Randall Lee,Whitesides, George M.
, p. 2379 - 2386 (2008/10/08)
trans-(Me3P)2Pt(CH2C(CH3) 3)(SO3CF3) (L2PtNpTf, 1) reacts with benzene-d6 at 133°C and gives trans-(Me3P)2Pt(C6D5)(SO 3CF3) (2) and neopentane-d1 as the major products. When this reaction is carried out in concentrated solutions ([1]0 ≥ 0.04 M), small quantities of neopentane-d0 (8-17%) and 1,1-dimethylcyclopropane (1-3%) are also detected; larger quantities of neopentane-d0 are produced (32-45%) when the initial concentration of 1 is low ([1]0 = 0.01-0.03 M). The rate of reaction is decreased by the addition of Bu4N+Tr- and increased by the addition of Bu4N+BF4-. A competitive kinetic isotope effect was estimated by allowing 1 to react with C6D5H and comparing the relative yields of neopentane-d0 and neopentane-d1: kH/kD is large, but its quantitative value is uncertain because of experimental ambiguities. The mechanism for this reaction seems to involve generation of L2PtNp+ as an essential intermediate. This intermediate appears to react with benzene by direct oxidative addition of a C-H bond, but electrophilic attack on the benzene ring cannot be rigorously excluded.