Reductive Elimination from Platinum(IV) Aminotroponiminate Dimethyl Complexes Promoted by Sterically Hindered Lewis Bases
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https://figshare.com/articles/dataset/Reductive_Elimination_from_Platinum_IV_Aminotroponiminate_Dimethyl_Complexes_Promoted_by_Sterically_Hindered_Lewis_Bases/2431819
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资源简介：
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].
创建时间：
2013-03-25
