1,3-Disila-2-gallata- and -indataallenic Anions [>SiMSi<]-.Li+ (M = Ga, In): compounds featuring double bonds between elements of groups 13 and 14

Norio Nakata; Rika Izumi; Vladimir Ya Lee; Masaaki Ichinohe; Akira Sekiguchi

doi:10.1021/ja040001h

1,3-Disila-2-gallata- and -indataallenic Anions [>SiMSi<]-.Li+ (M = Ga, In): compounds featuring double bonds between elements of groups 13 and 14

J Am Chem Soc. 2004 Apr 28;126(16):5058-9. doi: 10.1021/ja040001h.

Authors

Norio Nakata¹, Rika Izumi, Vladimir Ya Lee, Masaaki Ichinohe, Akira Sekiguchi

Affiliation

¹ Department of Chemistry, University of Tsukuba, Ibaraki, Japan.

PMID: 15099075
DOI: 10.1021/ja040001h

Abstract

The first compounds containing Si=Ga or Si=In double bonds, 1,3-disila-2-gallata- (2-) and -indataallenic anions (3-), were obtained in the form of lithium salts as dark red crystals by the reaction of bis(di-tert-butylmethylsilyl)dilithiosilane 1 with GaCl3 or InCl3. X-ray crystallographic analysis of 2-.[Li(thf)4]+ and 3-.[Li(thf)4]+ showed that the >SiMSi< frameworks (M = Ga, In) are not linear and the two Si=M bond lengths are about 9% shorter than typical Si-M single bonds. In the 29Si NMR spectra, the signals of the terminal Si atoms in 2- and 3- are greatly shifted upfield (2-: -79.9; 3-: -77.6 ppm). The NPA charge distribution for the model compound, [(Me3Si)2SiGaSi(SiMe3)2]- (4-) showed a large part of the negative charge localizing on the two terminal silicon atoms (-0.736 and -0.729). In addition, 2-.[Li(thf)4]+ reacted with MeI to give the corresponding iodogallane 5 nearly quantitatively. This result confirms that the allenic [>SiMSi<]- fragments are highly polarized.