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A bimetallic 1,1’-bis(boratabenzene) complex: unprecedented intramolecular metal-metal communication through a B-B bond

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posted on 2023-06-09, 01:07 authored by Holger Braunschweig, Serhiy Demeshko, William C Ewing, Ivo Krummenacher, Bret B Macha, James D Mattock, Franc Meyer, Jan Mies, Marius Schäfer, Alfredo VargasAlfredo Vargas
We report the synthesis of the first 1,1’-bis (boratabenzene) species by tetrabromodiborane(4) induced ring-expansion reactions of cobaltocene. Six equivalents of cobaltocene are required as the species plays the dual role of reagent as well as reductant to yield [{(?5-C5H5)Co}2{µ:?6,?6-(BC5H5)2}]. X-ray crystallographic analysis shows that the compound consists of coplanar BC5H5 rings which are coordinated on opposite faces to two cyclopentadienyl cobalt moieties, resulting in a trans-configured bimetallic complex. The formally dianionic bis(boratabenzene) moiety with a boron-boron single bond can be viewed as a symmetric dimer of the parent boratabenzene anion as well as the first example of a diboron analogue of biphenyl. The solution electrochemistry of the bimetallic complex shows four stepwise redox events, indicating significant intramolecular interaction between the cobalt ions across the 1,1’-bis(boratabenzene) unit. The magnetic properties, as investigated by variable-temperature SQUID magnetometry, reveal weak intramolecular antiferromagnetic interactions (J = -6.0 cm-1). Density Functional Theory calculations support the experimental results and add insights into the various electronic states of the complex.

History

Publication status

  • Published

File Version

  • Accepted version

Journal

Angewandte Chemie International Edition

ISSN

1521-3773

Publisher

Wiley

Issue

27

Volume

55

Page range

7708-7711

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2016-06-06

First Open Access (FOA) Date

2017-05-31

First Compliant Deposit (FCD) Date

2016-06-09

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