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Issue 8, 2010
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Synthesis and electrochemistry of some ferrocenyl substituted dicarba- and tricarbaborane compounds

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Abstract

Treatment of arachno-4-Me2S-B9H13 (1) with ethynylferrocene, FcC[triple bond, length as m-dash]CH (Fc = ferrocenyl), in boiling benzene afforded an inseparable 2 : 1 mixture of 6-Fc-nido-5,6-C2B8H11 (2a) and 5-Fc-nido-5,6-C2B8H11 (2b) in a 10% yield. However, compound 2b was converted quantitatively to the pure, violet 2a by the action of proton sponge (PS), followed by acidification. The structure of 2a was determined by X-ray diffraction analysis. Heating of 2a at 400 °C led to the dehydrogenation and isolation of the orange 1-Fc-closo-1,10-C2B8H9 (3) in almost quantitative yield, while treatment of 2a with t-BuNC and PS (proton sponge = 1,8-bis(dimethylamino)naphthalene) in CH2Cl2 generated the neutral absolute tautomer 7-t-BuNH-8-Fc-7,8,9-C3B8H10 (N4) (yield 50%), which could be converted quantitatively into the zwitterionic tautomer 7-t-BuNH2-8-Fc-7,8,9-C3B8H9 (Z4) via dissolution in MeCN. Tautomers N4 and Z4 sharply differ in NMR properties and both gave rise to a pair of cage-isomeric closo ferratricarbollides, [1-Cp-2-Fc-12-t-BuNH-1,2,4,12-FeC3B8H9] (5a) (Cp = η5-C5H5) (yield 48%) and [1-Cp-2-Fc-10-t-BuNH-1,2,4,10-FeC3B8H9] (5b) (yield 32%), upon heating with [CpFe(CO)2]2 in mesitylene at reflux. Electrochemical studies revealed that the compounds display one (compounds 2a and 3) or two (compounds 5a and 5b) well-defined, reversible one-electron Fe(II)/Fe(III) redox changes.

Graphical abstract: Synthesis and electrochemistry of some ferrocenyl substituted dicarba- and tricarbaborane compounds

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Article information


Submitted
22 Sep 2009
Accepted
16 Nov 2009
First published
13 Jan 2010

Dalton Trans., 2010,39, 2057-2061
Article type
Paper

Synthesis and electrochemistry of some ferrocenyl substituted dicarba- and tricarbaborane compounds

J. Holub, B. Štíbr, P. Štěpnička and I. Císařová, Dalton Trans., 2010, 39, 2057
DOI: 10.1039/B919767B

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