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C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0): Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift
快乐英文luraCalculations of a μ-Phosphanido Diplatinum(II)
Platform
期刊名称： Organometallicsconi
作者： Andreas Berkefeld,Marc Reimann,Gerald Hrner,Martin Kaupp,Hartmut
西班牙斗牛士吉他谱Schubert
年份： 2020年
摘要：Transition-metal phosphanides M–PR 2 are key intermediates in catalytic
struts
C–P bond functionalization. M–PR 2 formation from tertiary phosphines through P–日文培训
安妮海瑟薇奥斯卡
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C bond cleavage widens the scope beyond P–H functionalized substrates, but mechanistic understanding of this reaction still is fragmentary. Starting from a defined coordination complex has allowed monitoring the reaction of a Pt-PPh 3 moiety and Pt(0) by NMR spectroscopy. Initial Pt(0) transfer is rate-limiting and
leads to products from PPh 3 -borne ortho -C–H and C–P bond cleavage along kinetically distinct pathways. Albeit kinetically favored, the reversibility of C–H bond cleavage eventually leads to thermodynamically preferred C–P bond scission. This pathway affords a robust [Pt(μ-PPh 2 )Pt] core structure who redox chemistry
and reactivity
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