The Effect of Substituents at Lewis Acidic Bismuth(III) Centers on Its Propensity to Bind a Noble Metal Donor

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• 作者：Carolin Tschersich ; Santina Hoof ; Nicolas Frank ; Christian Herwig ; Christian Limberg
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 15, 2016
• 年：2016
• 卷：55
• 期：4
• 页码：1837-1842
• 全文大小：317K
• ISSN：1520-510X

文摘

To investigate the effect of X in ambiphilic compounds BiX(o-PPh₂-C₆H₄)₂, PBiP-X, on metallophilic Pt–Bi interactions in its PtCl₂ complexes two new derivatives PBiP-Me and PBiP-C₆F₅ were synthesized. Reaction with dichloro(1,5-cyclooctadiene)platinum(II) led to the platinum(II) complexes [PtCl₂(PBiP-Me)], 3, and [PtCl₂(PBiP-C₆F₅)], 4, which together with the halide [PtCl₂(PBiP-Cl)], 2, reported previously, establish a series of related PBiP-X complexes differing only in X. This could be complemented by accessing [PtCl₂(PBiP-OTf)], 5, through the reaction of 2 with AgOTf. Analysis of the geometrical and electronic structures of these complexes revealed that in all cases the platinum(II) centers act as donors (through their filled d_z² orbitals) to the bismuth(III) centers (possessing σ*(Bi-X)/6p acceptor orbitals). The strength of these interactions increases with increasing electron-withdrawing character of X, which supports the conceptual approach in constructing this new class of compounds.