DIRECT ELECTROCHEMICAL SYNTHESIS OF X2INCH2X COMPOUNDS (X = BR, I) AND A STUDY OF THEIR COORDINATION CHEMISTRY

被引:35
作者
ANNAN, TA
TUCK, DG
KHAN, MA
PEPPE, C
机构
[1] UNIV WINDSOR,DEPT CHEM & BIOCHEM,WINDSOR N9B 3P4,ONTARIO,CANADA
[2] UNIV OKLAHOMA,DEPT CHEM,NORMAN,OK 73019
[3] UNIV FED PARAIBA,CCEN,DEPT QUIM,CIDADE UNIV,BR-58000 JOAO PESSOA,PARAIBA,BRAZIL
关键词
D O I
10.1021/om00053a018
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The electrochemical oxidation of indium in CH2X2/CH3CN media (X = Cl, Br, I) gives InX. Indium(I) chloride disproportionates, but InBr or InI react with CH2X2 to give X2InCH2X (X = Br, I) derivatives. Treatment of the latter with Et4NX gives the 1:1 electrolytes Et4N[X3InCH2X]. With triphenylphosphine, Br2InCH2Br forms the phosphonium ylid derivative Br3InCH2P(C6H5)3, whose structure has been established by X-ray crystallography: cell constants a = 14.076 (4) angstrom, b = 7.610 (2) angstrom, c = 12.931 (2) angstrom; space group Pna2(1); R = 0.034, R(w) = 0.034. Reaction between N,N,N',N'-tetramethylethanediamine (tmen) and Br2InCH2Br also gives a cyclized nitrogen ylid Br3 activated InCH2NMe2CH2NMe2: cell constants a = 12.814 (3) angstrom, b = 15.721 (4) angstrom, c = 21.343 (5) angstrom; space group Pbca; R = 0.045, R(w) = 0.047. The iodo species I2InCH2I undergoes redistribution in solution, and two tmen derivatives were isolated, I3 activated InCH2NMe2CH2NMe2 and [I activated In(CH2NMe2CH2NMe2)2](I)2. The latter has two identical cyclized ylid ligands: a = 11.414 (4) angstrom, b = 14.592 (6) angstrom, c = 16.144 (7) angstrom, beta = 110.1 (4)-degrees; space group P2(1)/c; R = 0.051, R(w) = 0.051. The H-1 and C-13 NMR spectra show that the CH2 group in X2InCH2X is electron-poor, in keeping with the tendency for nucleophilic ligands to react at this site as well as at the metal.
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页码:2159 / 2166
页数:8
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