Binary Si/N-[4.4]-Spirocycles with Two SiH2SiH2 Loops
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- 作者：Marcus Sö ; ldner ; Annette Schier ; and Hubert Schmidbaur
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：February 9, 1998
- 年：1998
- 卷：37
- 期：3
- 页码：510 - 515
- 全文大小：145K
- 年卷期：v.37,no.3(February 9, 1998)
- ISSN：1520-510X
文摘
Tetra(alkylamino)silanes Si(NHR)4 withR = Me, n-Pr, n-Bu, and i-Pr(1a-d) have been prepared viaimprovedmethods and characterized by complementary analytical and spectroscopicdata. The reaction of 1a-c with2equiv of Tf-SiH2SiH2-Tf (Tf =trifluoromethylsulfonyloxy, "triflate") and triethylamine intoluene gives goodyields of the spirocyclic compounds[(SiH2NR)2]2Si(2a-c). 2a isobtained as a crystalline, but highly volatile,product (mp 35 
C, bp0.05 46-47 C), the crystal andmolecular structure of which has been determined bysingle-crystal X-ray diffraction methods (monoclinic, space groupP21/n, Z = 8). Thelattice contains twoindependent molecules in the asymmetric unit, which have very similardimensions. The two five-memberedrings are almost planar and close to perpendicular to each other.Owing to sterical hindrance, the analogousreaction of 1d gives only low yields of the correspondingspirocycle{[SiH2N(i-Pr)]2}2Si,2d. A silylammoniumsalt{[SiH2N(i-Pr)]2Si-[NH(i-Pr)]-[NH2(i-Pr)]}+Tf-(3) is produced as a major product. Compound3 is one ofthe very few silylammonium salts as confirmed by a full structuralanalysis (monoclinic, space groupP21/c, Z =4). In the crystal, 2 equiv are grouped together as acentrosymmetrical cluster of two cations and two anionswith hydrogen bonds between the amino/ammonio and the sulfonate groups.Equimolar quantities of 1d and the1,2-disilanediylbis(triflate) in the presence of NEt3give good yields of the monocyclic compound[SiH2N(i-Pr)]2Si[NH(i-Pr)]2, 4.Compounds 1a-d and2a-c are hydrogen- and silicon-richprecursor molecules for the productionof silicon nitride in pyrolytic, plasma- or laser-induced (thermal)decomposition and for the preparation of silazanenetworks and gels by controlled aminolysis or by metathesis of theSi-Si bonds.
C, bp0.05 46-47 C), the crystal andmolecular structure of which has been determined bysingle-crystal X-ray diffraction methods (monoclinic, space groupP21/n, Z = 8). Thelattice contains twoindependent molecules in the asymmetric unit, which have very similardimensions. The two five-memberedrings are almost planar and close to perpendicular to each other.Owing to sterical hindrance, the analogousreaction of 1d gives only low yields of the correspondingspirocycle{[SiH2N(i-Pr)]2}2Si,2d. A silylammoniumsalt{[SiH2N(i-Pr)]2Si-[NH(i-Pr)]-[NH2(i-Pr)]}+Tf-(3) is produced as a major product. Compound3 is one ofthe very few silylammonium salts as confirmed by a full structuralanalysis (monoclinic, space groupP21/c, Z =4). In the crystal, 2 equiv are grouped together as acentrosymmetrical cluster of two cations and two anionswith hydrogen bonds between the amino/ammonio and the sulfonate groups.Equimolar quantities of 1d and the1,2-disilanediylbis(triflate) in the presence of NEt3give good yields of the monocyclic compound[SiH2N(i-Pr)]2Si[NH(i-Pr)]2, 4.Compounds 1a-d and2a-c are hydrogen- and silicon-richprecursor molecules for the productionof silicon nitride in pyrolytic, plasma- or laser-induced (thermal)decomposition and for the preparation of silazanenetworks and gels by controlled aminolysis or by metathesis of theSi-Si bonds.