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硼二价基和乙硼烷(4)-1,2-二价基桥连的铂 A 型框架配合物

Boranediyl- and Diborane(4)-1,2-diyl-Bridged Platinum A-Frame Complexes.

作者信息

Brunecker Carina, Müssig Jonas H, Arrowsmith Merle, Fantuzzi Felipe, Stoy Andreas, Böhnke Julian, Hofmann Alexander, Bertermann Rüdiger, Engels Bernd, Braunschweig Holger

机构信息

Institut für Anorganische Chemie and, Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Wüzburg, Am Hubland, 97074, Würzburg, Germany.

Institut für Physikalische und Theoretische Chemie, Julius-Maximilians-Universität Würzburg, Emil-Fischer-Straße 42, 97074, Würzburg, Germany.

出版信息

Chemistry. 2020 Jul 14;26(39):8518-8523. doi: 10.1002/chem.202001168. Epub 2020 Jun 17.

Abstract

Diplatinum A-frame complexes with a bridging (di)boron unit in the apex position were synthesized in a single step by the double oxidative addition of dihalo(di)borane precursors at a bis(diphosphine)-bridged Pt complex. While structurally analogous to well-known μ-borylene complexes, in which delocalized dative three-center-two-electron M-B-M bonding prevails, theoretical investigations into the nature of Pt-B bonding in these A-frame complexes show them to be rare dimetalla(di)boranes displaying two electron-sharing Pt-B σ-bonds. This is experimentally reflected in the low kinetic stability of these compounds, which are prone to loss of the (di)boron bridgehead unit.

摘要

通过在双(二膦)桥连的铂配合物上对二卤(二)硼烷前体进行双氧化加成,一步合成了在顶端位置带有桥连(二)硼单元的双铂A框架配合物。虽然在结构上与著名的μ-硼烯配合物类似,其中离域的给体三中心双电子M-B-M键占主导,但对这些A框架配合物中Pt-B键本质的理论研究表明,它们是罕见的双金属(二)硼烷,具有两个共享电子的Pt-B σ键。这在实验中表现为这些化合物的低动力学稳定性,它们容易失去(二)硼桥头单元。

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