Reductive Elimination from Platinum(IV) Aminotroponiminate Dimethyl Complexes Promoted by Sterically Hindered Lewis Bases

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 (...

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Published in:Organometallics 2013-03, Vol.32 (6), p.1938-1950
Main Authors: Traversa, Elise, Templeton, Joseph L, Cheng, Hiu Yan, Mohadjer Beromi, Megan, White, Peter S, West, Nathan M
Format: Article
Language:English
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Summary: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(CH3)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(PPh2Me)(SMe2)][OTf] (6c) reductively eliminates [PMe2Ph2][OTf] or [SMe3][OTf] to form the PtII 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 [MePCy3][OTf].
ISSN:0276-7333
1520-6041
DOI:10.1021/om400034y