期刊
DALTON TRANSACTIONS
卷 44, 期 21, 页码 9860-9871出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt01293g
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资金
- Russian Foundation for Basic Research [12-03-00772, 13-03-00581]
- Russian Academy of Sciences
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)(2)O, 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, N-3). 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.
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