nido-Carborane-Containing Compounds Resulting from the Reaction of closo-Carboranes with Transition Metal Complexes

Francesc Teixidor, Clara Viñas, Reijo Sillanpää, Raikko Kivekäs, Jaume Casabó

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Abstract

The reaction of closo derivatives of 1,2-dithio-1,2-dicarba-closo-dodecaborane with [MCl(PPh3)2] (M = Cu, Ag) in ethanol, produces complexes of the corresponding nido derivatives of 7,8-dithio-7,8-dicarba-mVo-undecaborate- (1-). These nido ligands form via formal B+ elimination in the closo precursors, becoming anionic, i.e., they have a negative charge which greatly enhances their coordinating capabilities. As a consequence, the dithio closo derivatives which are neutral dithioethers, and hence weak ligands, tend to modify themselves upon coordination, losing a boron atom and becoming anionic, to produce the strongly coordinating 7,8-dithio-7,8-dicarba-nido-undecaborate(1-) derivative ligands. The B+ removal has been proven by the X-ray analysis of the resulting [Cu{7,8-µ-S(CH2CH2- OCH2CH2OCH2CH2)SC2B9H10}PPh3)] and [Ag{7,8-µ-S(CH2CH2OCH2CH2)SC2B9H10})PPh3)]. Crystal structure data for [Cu{7,8-µ-S(CH2CH2OCH2CH2OCH2CH2)SC2B9H10}(PPh3)]: mol wt 637.5; space group.P1 Z= 2; a = 10.880(3) Å, b = 12.784(3) Å, c = 13.707(5) Å, α = 64.31(2)°, β = 68.09(2)°, γ = 84.64(2)° RW(Fo) = 0.061. Crystal structure data for [Ag{7,8-µ-S(CH2CH2OCH2CH2)SC2B9H10}(PPh3)] mol wt 637.8, space group P21/n; Z =8; a = 14.578(9) Å, b = 23.557(9) Å, c = 18.322(6) Å, β = 108.73(3)°, RW(Fo) = 0.077. © 1994, American Chemical Society. All rights reserved.
Original languageEnglish
Pages (from-to)2645-2650
JournalInorganic Chemistry
Volume33
Issue number12
DOIs
Publication statusPublished - 1 Jun 1994

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