Carbon(0)-Bridged Pt/Ag Dinuclear and Tetranuclear Complexes Based on a Cyclometalated Pincer Carbodiphosphorane Platform

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• 作者：Kazuyuki KuboHiroyuki Okitsu ; Hiroto Miwa ; Shoko Kume ; Ronald G. Cavell ; Tsutomu Mizuta
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 23, 2017
• 年：2017
• 卷：36
• 期：2
• 页码：266-274
• 全文大小：539K
• ISSN：1520-6041

文摘

A carbon(0)-bridged Pt₂Ag₂ cluster was synthesized from the reaction of a cyclometalated pincer carbodiphosphorane platinum complex with AgOTf, by forming Pt(II)←C(0)→Ag(I) dative bonds along with Pt(II)–Ag(I) and Ag(I)–Ag(I) metal–metal interactions. X-ray diffraction analysis reveals that the cluster adopts an antiparallel sandwich structure with a ladder-shaped PtC/AgAg/CPt core. The coordination plane of the platinum unit is highly distorted due to the in-plane steric repulsion between the PEt₃ ligand on the platinum and the nearest proton on each of the two cyclometalated phenyl rings in the pincer carbodiphosphorane framework. The cluster is very labile and displays different reactivity patterns toward trivalent phosphorus ligands. In the reaction with bulky PPh₃, a dinuclear complex was formed because of coordination of PPh₃ to the silver atom upon cleavage of the tetranuclear core. In contrast, replacement of the PEt₃ on the platinum center by P(OPh)₃, which is sterically less demanding, led to a dinuclear complex where the eliminated PEt₃ ligand recoordinated to the silver atom.