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

Gobika Thiripuranathar, Wing Y. Man, Cesar Palmero Palos, Antony P Y Chan, Bernhard T Leube, David Ellis, David McKay, Stuart A. Macgregor, Laure Jourdan, Georgina M. Rosair, Alan J. Welch

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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.

Original languageEnglish
Pages (from-to)5628-5637
Number of pages10
JournalDalton Transactions
Volume44
Issue number12
DOIs
Publication statusPublished - 28 Mar 2015

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    Thiripuranathar, G., Man, W. Y., Palmero Palos, C., Chan, A. P. Y., Leube, B. T., Ellis, D., McKay, D., Macgregor, S. A., Jourdan, L., Rosair, G. M., & Welch, A. J. (2015). Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane). Dalton Transactions, 44(12), 5628-5637. https://doi.org/10.1039/c5dt00081e