Mondal Bijan, Bag Ranjit, Ghorai Sagar, Bakthavachalam K, Jemmis Eluvathingal D, Ghosh Sundargopal
Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, India.
Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore, 560012, India.
Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8079-8083. doi: 10.1002/anie.201803154. Epub 2018 May 28.
The reaction of [(CpMo) (μ-Cl) B H ] (1) with CO at room temperature led to the formation of the highly fluxional species [{CpMo(CO) } {μ-η :η -B H }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) } C H ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) ] fragment, [{CpMo(CO) } B H W(CO) ] (3) was isolated upon treatment with [W(CO) ⋅thf]. Compound 3 shows the intriguing presence of [B H ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{CpW(CO) } B H W(CO) ] (4) and [{Cp*W(CO) } B H Mo(CO) ] (5), which provided direct proof of the existence of the tungsten analogue of 2.
[(CpMo)(μ-Cl)BH]（1）在室温下与CO反应生成了高度易变的物种[{CpMo(CO)} {μ-η:η -BH}]（2）。据我们所知，化合物2是符合单桥C结构的双金属二硼烷（4）的首个例子。理论研究表明，2模拟了科顿双钼-炔烃配合物[{CpMo(CO)}CH]。为了用2e [W(CO)]片段取代2中二硼烷（4）的两个氢原子，在用[W(CO)·thf]处理后分离得到了[{CpMo(CO)}BHW(CO)]（3）。化合物3显示出有趣的[BH]存在，其B-B短键长为1.624(4) Å。我们分离得到了3的钨类似物[{CpW(CO)}BHW(CO)]（4）和[{Cp*W(CO)}BHMo(CO)]（5），这直接证明了2的钨类似物的存在。
