PBiP Pincer Complexes of Platinum, Palladium, and Iridium Featuring Metal鈥揗etal Bonds Synthesized by Oxidative Addition of Bismuth鈥揌alide Bonds

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• 作者：Carolin Tschersich ; Beatrice Braun ; Christian Herwig ; Christian Limberg
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 10, 2015
• 年：2015
• 卷：34
• 期：15
• 页码：3782-3787
• 全文大小：292K
• ISSN：1520-6041

文摘

The compound BiCl(o-PPh₂-C₆H₄)₂, PBiP-Cl, which in previous work had been shown to form complexes with pronounced M鈫?/b>Bi character, when metal(I) ions of group 11 or Pt^II and Pd^II ions were coordinated, behave differently in contact with late metal atoms in low oxidation states, known to easily undergo oxidative additions: Treatment of PBiP-Cl with M(PPh₃)₄, with M = Pt, Pd, led to the formal insertion of M into the Bi鈥揅l bond to yield complexes [MCl(PBiP)]. Analogues PBiP-X with X = Br, I that could be accessed behaved similarly, producing [MX(PBiP)]. Both types of complexation reactions鈥攃oordination of PBiP-Cl as an ambiphilic ligand and oxidative addition鈥攚ere observed to occur when [Ir(acac)(cod)] was chosen as the precursor compound. NMR investigations clearly indicated the presence of [Ir^I(acac)(PBiP-Cl)] and [Ir^III(acac)Cl(PBiP)] beside each other in solution, from which, however, only [Ir^III(acac)Cl(PBiP)] could be crystallized. DFT results showed that both products differ only slightly in energy. Reaction of PBiP-Cl with [Ir(acac-F₆)(cod)] led only to the iridium(III) product, underlining that electronic effects sensitively influence the course of reactivity and the position of the equilibrium.