1334306-85-2Relevant academic research and scientific papers
Carbon-hydrogen bond cleavage reaction in four-coordinate (2,6-dimethylbenzenethiolato)platinum(II) complexes. dramatic acceleration by thiolato hydrogen acceptor
Hirano, Masafumi,Tatesawa, Shin-Ya,Yabukami, Minoru,Ishihara, Yoko,Hara, Yusuke,Komine, Nobuyuki,Komiya, Sanshiro
, p. 5110 - 5122 (2011/11/07)
The (2,6-dimethylbenzenethiolato)platinum(II) complexes PtR(SC 6H3Me2-2,6-κ1S)L2 (R = Me, L = PMe3 (1a), PPh3 (1c), L2 = dppe (1d), dppp (1e); R = Et, L = PPh3 (2c); R = CH2CMe 3, L = PPh3 (3c)) and Pt(SC6H 3Me2-2,6-κ1S)2L2 (L = PMe3 (4a), PEt3 (4b), PPh3 (4c), L 2 = dppe (4d), dppp (4e), dppb (4f)) have been prepared. Heating of these compounds results in an internal sp3 C-H bond cleavage reaction, giving the thiaplatinacycle complexes Pt[SC6H 3(CH2-2)(Me-6)-κ2S,C]L2 (L = PMe3 (5a), PEt3 (5b), PPh3 (5c), L2 = dppe (5d), dppp (5e), dppb (5f)) in moderate to quantitative yields. The reactions of 1c and 4c proceed via prior dissociation of PPh3, and a concerted mechanism is proposed. Of particular interest is the sp3 C-H bond activation step, whose observed rate constant for 4c is no less than 104-fold faster than that for 1c. The arenethiolato group is expected to enhance the C-H bond cleavage step as a hydrogen acceptor.
