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Braunschweig, Holger; Demeshko, Serhiy; Ewing, William C; Krummenacher, Ivo; Macha, Bret B; Mattock, James D; Meyer, Franc; Mies, Jan; Schäfer, Marius; Vargas, Alfredo (2016)
Publisher: Wiley
Languages: English
Types: Article
Subjects: QD
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 [{(η5-C5H5)Co}2{μ:η6,η6-(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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    • E1/2(2)=0.94^^V, E1/2(3)=2.09^^V, and E1/2(4)=2.36^^V
    • (relative to the Fc/Fc+ couple; Fc=[(η5-C5H5)2Fe]).
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