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Synthesis and Electrochemical Behavior of Mixed Organoboron/Organomercury Compounds
Author(s) -
Melaimi Mohand,
Gabbaï François P.
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200098
Subject(s) - chemistry , boron , organomercury , electrochemistry , atomic orbital , natural bond orbital , lewis acids and bases , organoboron compounds , inorganic chemistry , crystallography , stereochemistry , medicinal chemistry , computational chemistry , metal , density functional theory , organic chemistry , catalysis , electron , electrode , physics , quantum mechanics
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) 2 C 6 F 4 and 1, 3‐(HgCl) 2 C 6 F 4 , respectively. The resulting tetranuclear B 2 Hg 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 σ 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.