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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] and [{Cp*M(CO) 2 } 2 B 2 H 2 M(CO) 4 ], M=Mo,W

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] and [{CpM(CO) 2 } 2 B 2 H 2 M(CO) 4 ], M=Mo,W

Bijan Mondal, Ranjit Bag, Sagar Ghorai, K Bakthavachalam, Eluvathingal D Jemmis, Sundargopal Ghosh

Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8079-8083.

PMID: 29697175

Abstract:

The reaction of [(Cp*Mo)2 (μ-Cl)2 B2 H6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] (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 }2 C2 H2 ]. 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 B2 H2 W(CO)4 ] (3) was isolated upon treatment with [W(CO)5 ⋅thf]. Compound 3 shows the intriguing presence of [B2 H2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2 }2 B2 H2 W(CO)4 ] (4) and [{Cp*W(CO)2 }2 B2 H2 Mo(CO)4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2.

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Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] and [{Cp*M(CO) 2 } 2 B 2 H 2 M(CO) 4 ], M=Mo,W

Abstract:

Chemicals Related in the Paper:

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{CpMo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] and [{CpM(CO) 2 } 2 B 2 H 2 M(CO) 4 ], M=Mo,W