Issue 12, 2015

Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

Abstract

Examples of singly-metallated derivatives of 1,1′-bis(o-carborane) have been prepared and spectroscopically and structurally characterised. Metallation of [7-(1′-1′,2′-closo-C2B10H11)-7,8-nido-C2B9H10]2− with a {Ru(p-cymene)}2+ fragment affords both the unisomerised species [1-(1′-1′,2′-closo-C2B10H11)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (2) and the isomerised [8-(1′-1′,2′-closo-C2B10H11)-2-(p-cymene)-2,1,8-closo-RuC2B9H10] (3), and 2 is easily transformed into 3 with mild heating. Metallation with a preformed {CoCp}2+ fragment also affords a 3,1,2-MC2B9-1′,2′-C2B10 product [1-(1′-1′,2′-closo-C2B10H11)-3-Cp-3,1,2-closo-CoC2B9H10] (4), but if CoCl2/NaCp is used followed by oxidation the result is the 2,1,8-CoC2B9-1′,2′-C2B10 species [8-(1′-1′,2′-closo-C2B10H11)-2-Cp-2,1,8-closo-CoC2B9H10] (5). Compound 4 does not convert into 5 in refluxing toluene, but does do so if it is reduced and then reoxidised, perhaps highlighting the importance of the basicity of the metal fragment in the isomerisation of metallacarboranes. A computational study of 1,1′-bis(o-carborane) is in excellent agreement with a recently-determined precise crystallographic study and establishes that the {1′,2′-closo-C2B10H11} fragment is electron-withdrawing compared to H.

Graphical abstract: Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

Supplementary files

Article information

Article type
Paper
Submitted
08 Jan 2015
Accepted
09 Feb 2015
First published
09 Feb 2015
This article is Open Access
Creative Commons BY license

Dalton Trans., 2015,44, 5628-5637

Author version available

Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

G. Thiripuranathar, W. Y. Man, C. Palmero, A. P. Y. Chan, B. T. Leube, D. Ellis, D. McKay, S. A. Macgregor, L. Jourdan, G. M. Rosair and A. J. Welch, Dalton Trans., 2015, 44, 5628 DOI: 10.1039/C5DT00081E

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