Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO)2}2{μ‐η2:η2‐B2H4}] and [{CpM(CO)2}2B2H2M(CO)4], M=Mo,W

• Published in: Angewandte Chemie International Edition 2018-07, Vol.57 (27), p.8079-8083
• Main Authors: Mondal, Bijan, Bag, Ranjit, Ghorai, Sagar, Bakthavachalam, K., Jemmis, Eluvathingal D., Ghosh, Sundargopal
• Format: Article
• Language: English
• Subjects: Alkynes; Bimetals; chemical bonding; Coordination compounds; Cotton; Diborane; diborene; Hydrogen atoms; Metal complexes; molybdenum; Tungsten
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201803154

The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] (3) was isolated upon treatment with [W(CO)5⋅thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2}2B2H2W(CO)4] (4) and [{Cp*W(CO)2}2B2H2Mo(CO)4] (5), which provided direct proof of the existence of the tungsten analogue of 2. Different ways 2 B special: Dinuclear Group 6 metal complexes of diborane(4) and diborene(2) in unusual bonding situations have been synthesized (see core structures). The highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] was found to mimic the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. Treatment with [W(CO)5⋅thf] gave [{Cp*Mo(CO)2}2B2H2W(CO)4] containing [B2H2] with a short B−B length of 1.624(4) Å.