1426064-63-2Relevant academic research and scientific papers
Reductive elimination from platinum(IV) aminotroponiminate dimethyl complexes promoted by sterically hindered lewis bases
Traversa, Elise,Templeton, Joseph L.,Cheng, Hiu Yan,Mohadjer Beromi, Megan,White, Peter S.,West, Nathan M.
, p. 1938 - 1950 (2013/05/09)
A series of PtII and PtIV aminotroponimate (ATI = N-tolyl-aminotroponiminate) complexes has been prepared. The PtII complex (ATI)Pt(CH3)(SMe2) (1a) is synthesized from the reaction of [Li][ATI] with (Me)(Cl)Pt(SMe2)2. Addition of either ethylene or carbon monoxide to 1a results in the formation of (ATI)Pt(CH3)(η2-C2H4) (1b) or (ATI)Pt(CH3)(CO) (1c), respectively. Oxidative addition of MeOTf or MeI to 1a results in formation of the PtIV complex [(ATI)Pt(CH 3)2(X)(SMe2)] (X = OTf (3), I (2)). Complex 3 reacts with isocyanides, which replace the triflate ligand to form [(ATI)Pt(CH3)2(CNR)(SMe2)][OTf] (4). Complex 3 also undergoes ligand substitution reactions with azide or cyanide to form (ATI)Pt(CH3)2(N3)(SMe2) (5a) or (ATI)Pt(CH3)2(CN)(SMe2) (5b). Addition of PR3 results in the substitution product [(ATI)Pt(CH3) 2(PR3)(SMe2)][OTf] for phosphines with cone angles ≤136 (P(OMe)3, PMe3, PMe2Ph). The PtIV complex [(ATI)Pt(CH3)2(PPh 2Me)(SMe2)][OTf] (6c) reductively eliminates [PMe 2Ph2][OTf] or [SMe3][OTf] to form the Pt II complex (ATI)Pt(CH3)(PPh2Me) (7a) in solution at room temperature. Addition of 1 equiv of PPh3, which has a cone angle of 145, results in the formation of 50% of PtII(ATI) Pt(CH3)(PR3) and [MePPh3][OTf]. Reaction of 3 with PCy3, which has a cone angle of 170, yields complete and immediate conversion to (ATI)Pt(CH3)(SMe2) and [MePCy 3][OTf].
