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A bimetallic 1,1’-bis(boratabenzene) complex: unprecedented intramolecular metal-metal communication through a B-B bond
journal contribution
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 VargasWe 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.
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Publication status
- Published
File Version
- Accepted version
Journal
Angewandte Chemie International EditionISSN
1521-3773Publisher
WileyExternal DOI
Issue
27Volume
55Page range
7708-7711Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2016-06-06First Open Access (FOA) Date
2017-05-31First Compliant Deposit (FCD) Date
2016-06-09Usage metrics
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