Brunecker Carina, Müssig Jonas H, Arrowsmith Merle, Fantuzzi Felipe, Stoy Andreas, Böhnke Julian, Hofmann Alexander, Bertermann Rüdiger, Engels Bernd, Braunschweig Holger
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.
Chemistry. 2020 Jul 14;26(39):8518-8523. doi: 10.1002/chem.202001168. Epub 2020 Jun 17.
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.
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。
