1,2-Disilanediyl Bis(triflate), F3CSO3-SiH2SiH2-O 3SCF3, as the Key Intermediate for a Facile Preparation of Open-Chain and Cyclic 1,1- and 1,2-Diaminodisilanes

Marcus Söldner, Annette Schier, Hubert Schmidbaur

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Abstract

Convenient high-yield syntheses for several open-chain and cyclic diaminodisilanes with fully hydrogenated Si-Si linkages are reported. The key intermediate for the preparation of the title compounds, 1,2-bis(((trifluoromethyl)-sulfonyl)oxy)disilane (1), reacts with 2 equiv of diethylamine to afford a mixture of the isomers Et2NSiH2SiH2NEt2 (2a) and (Et2N)2SiHSiH3 (2a′). Isopropylamine and 1 give iPr2NSiH2SiH2NiPr 2 (2b) exclusively. Treatment of 1 with 1 equiv of a primary alkylamine affords 2,3,5,6-tetrasilapiperazines [RNSiH2SiH2RNSiH2SiH2; R = iPr (3a), tBu (3b), Bzl (3c)] comprising two SiH2-SiH2 linkages. 1,3-Bifunctional bis(isopropylamino)silanes [(iPrNH)2SiR2; R = Me, Ph] were found to react with 1 to give trisilaimidazolidines [(iPrN)SiR2(iPrN)SiH2SiH 2; R = Me (4a), Ph (4b)] again comprising the N-SiH2-SiH2-N unit. The crystal structures of N,N′-diisopropyl-2,2-diphenyl-2,4,5-trisilaimidazolidine (4b) and N,N′-di-tert-butyl-2,3,5,6-tetrasilapiperazine (3b) were determined in X-ray diffraction studies; the five-membered ring of 4b is nearly planar with all nitrogen atoms in a planar configuration. The six-membered ring of 3b has a twist conformation, but again with the two nitrogen atoms in a planar configuration. Surprisingly, the treatment of 1 with 1,4-bifunctional N,N′-dialkylethylenediamines [(RNHCH2-)2; R = iPr, tBu] does not give the analogous six-membered-ring compounds but leads selectively to the isomeric five-membered heterocycles [(CH2NR)2SiHSiH3; R = iPr (5a), tBu (5b)], which are the products of a Si → Si hydrogen shift rearrangement.

Original languageEnglish
Pages (from-to)1758-1763
Number of pages6
JournalInorganic Chemistry
Volume36
Issue number9
DOIs
StatePublished - 23 Apr 1997
Externally publishedYes

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