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Issue 21, 2015
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Cyanide free contraction of disclosed 1,4-dioxane ring as a route to cobalt bis(dicarbollide) derivatives with short spacer between the boron cage and terminal functional group

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Abstract

The 1,4-dioxane derivative of cobalt bis(dicarbollide) reacts with dialkylsulfides and triphenylphosphine to give the corresponding sulfonium and phosphonium derivatives [8-L(CH2CH2O)2-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] (L = SMe2, S(CH2CH2)2O, PPh3). The treatment of the triphenylphosphonium derivative with sodium hydroxide results in contraction of the side chain with formation of [8-HOCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]. The same product was obtained by treatment of the dimethylsulfonium derivative with the poorly nucleophilic base t-BuOK, whereas the stronger nucleophiles induce the sulfur demethylation to give [8-MeS(CH2CH2O)2-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]. The alcohol was used for the synthesis of a series of other short-spacer functional derivatives [8-XOCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] (X = NH2, SH, N3). A similar contraction of the disclosed 1,4-dioxane ring via the reactions with SMe2 and PPh3 can be used for the synthesis of short-spacer functional derivatives of nido-carborane, whereas the 1,4-dioxane derivatives of closo-decaborate and closo-dodecaborate anions, being stronger electron donors, are more stable and do not react with dimethylsulfide and triphenylphosphine.

Graphical abstract: Cyanide free contraction of disclosed 1,4-dioxane ring as a route to cobalt bis(dicarbollide) derivatives with short spacer between the boron cage and terminal functional group

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Supplementary files

Article information


Submitted
03 Apr 2015
Accepted
07 Apr 2015
First published
13 Apr 2015

Dalton Trans., 2015,44, 9860-9871
Article type
Paper
Author version available

Cyanide free contraction of disclosed 1,4-dioxane ring as a route to cobalt bis(dicarbollide) derivatives with short spacer between the boron cage and terminal functional group

A. V. Shmal'ko, M. Yu. Stogniy, G. S. Kazakov, S. A. Anufriev, I. B. Sivaev, L. V. Kovalenko and V. I. Bregadze, Dalton Trans., 2015, 44, 9860
DOI: 10.1039/C5DT01293G

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