Synthesis and Electrochemical Behavior of Mixed Organoboron/Organomercury Compounds
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abstract
As part of our ongoing interest in the synthesis and reduction chemistry of organoboron species, we have investigated the synthesis of mixed organoboron/organomercury complexes by reaction of the Li(THF) 4 salt of dimesityl-1, 8-naphthalenediylborate with 1, 2-(HgCl) 2C 6F 4 and 1, 3-(HgCl) 2C 6F 4, respectively. The resulting tetranuclear B 2Hg 2 complexes (2 and 3, respectively) were characterized by multinuclear NMR spectroscopy and single-crystal X-ray analysis. The cyclic voltammogram of complex 2, which features a B-Hg-Hg-B core connected by an ortho-phenylene (Hg-Hg connection) and two peri-naphthalenediyl linkers (B-Hg connection), shows significant coupling of the two electroactive boryl units, presumably via a direct interaction of the vacant p orbitals of the four neighboring Lewis acids. This conclusion is supported by DFT calculations, which show that the LUMO of 2 spans the four Lewis acids, with a major in phase contribution from the boron 2p orbitals and the mercury 6p orbitals. Copyright 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.