Synthetic and Structural Study of the Coordination Chemistry of a peri-Backbone Supported Phosphino-Phosphonium Salt

Petr Kilian, Matthew James Ray, Michael Buehl, Laurence Taylor, Kasun Sankalpa Athukorala Arachchige, Alexandra Martha Zoya Slawin

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7 Citations (Scopus)

Abstract

Coordination chemistry of an acenaphthene peri-backbone-supported phosphino-phosphonium chloride (1) was investigated, revealing three distinct modes of reactivity. The reaction of 1 with Mo(CO)4(nor) gives the Mo(0) complex [(1)Mo(CO)4Cl] (2), in which the ligand 1 exhibits monodentate coordination through the phosphine donor and the P–P bond is retained. PtCl2(cod) reacts with the chloride and triflate salts of 1 to form a mononuclear complex [(1Cl)PtCl2] (3) and a binuclear complex [((1Cl)PtCl)2][2TfO] (4), respectively. In both of these complexes, the platinum center adds across the P–P bond, and subsequent chloride transfer to the phosphenium center results in phosphine-chlorophosphine bidentate coordination. [((1)PdCl)2] (5) was isolated from the reaction of 1 and Pd2(dba)3 (dba = dibenzylideneacetone). Oxidative addition to palladium(0) results in a heteroleptic phosphine bridging phosphide coordination to the Pd(II) center. In addition, reaction of 1 with BH3·SMe2 leads to the bis(borane) adduct of the corresponding mixed tertiary/secondary phosphine (6), with BH3 acting as both a reducing agent and a Lewis acid. The new compounds were fully characterized, including X-ray diffraction. The ligand properties of 1 and related bonding issues are discussed with help of DFT computations.
Original languageEnglish
Pages (from-to)8538−8547
Number of pages10
JournalInorganic Chemistry
Volume53
DOIs
Publication statusPublished - 29 Jul 2014

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