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Icosahedral metallacarborane/carborane species derived from 1,1[prime or minute]-bis(o-carborane)

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Date
28/03/2015
Author
Thiripuranathar, Gobika
Man, Wing Y.
Palmero, Cesar
Chan, Antony P. Y.
Leube, Bernhard T.
Ellis, David
McKay, David
Macgregor, Stuart A.
Jourdan, Laure
Rosair, Georgina M.
Welch, Alan J.
Keywords
QD Chemistry
DAS
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Abstract
Examples of singly-metallated derivatives of 1,1[prime or minute]-bis(o-carborane) have been prepared and spectroscopically and structurally characterised. Metallation of [7-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-7,8-nido-C2B9H10]2- with a {Ru(p-cymene)}2+ fragment affords both the unisomerised species [1-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (2) and the isomerised [8-(1[prime or minute]-1[prime or minute],2[prime or minute]-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[prime or minute],2[prime or minute]-C2B10 product [1-(1[prime or minute]-1[prime or minute],2[prime or minute]-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[prime or minute],2[prime or minute]-C2B10 species [8-(1[prime or minute]-1[prime or minute],2[prime or minute]-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[prime or minute]-bis(o-carborane) is in excellent agreement with a recently-determined precise crystallographic study and establishes that the {1[prime or minute],2[prime or minute]-closo-C2B10H11} fragment is electron-withdrawing compared to H.
Citation
Thiripuranathar , G , Man , W Y , Palmero , 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[prime or minute]-bis(o-carborane) ' , Dalton Transactions , vol. 44 , no. 12 , pp. 5628-5637 . https://doi.org/10.1039/C5DT00081E
Publication
Dalton Transactions
Status
Peer reviewed
DOI
https://doi.org/10.1039/C5DT00081E
ISSN
1477-9226
Type
Journal article
Rights
(c) 2015, the authors. This journal is (c) The Royal Society of Chemistry. This is an open access article licensed under a Creative Commons Attribution 3.0 Unported Licence.
Description
We thank ORSAS (GS) and the EPSRC (DE and DMcK supported by project EP/E02971X/1, WYM supported by project EP/I031545/1) for funding.
Collections
  • University of St Andrews Research
URL
http://dx.doi.org/10.1039/C5DT00081E
URI
http://hdl.handle.net/10023/8264

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