|
Polysilicon hydrides are polymers containing only silicon and hydrogen. They have the formula (SiHn)''x'' where n = 0.2 to 2.5 and ''x'' is the number of monomer units. The polysilicon hydrides are generally colorless or pale-yellow/ocher powders that are easily hydrolyzed and ignite readily in air. The surfaces of silicon prepared by MOCVD using silane (SiH4) consist of a polysilicon hydride. ==Synthesis== Polysilicon hydrides are much less thermally stable than the corresponding alkanes (CnH2n+2). They are kinetically labile, with their decomposition reaction rate increasing with increases in the number of silicon atoms in the molecule. Consequently, the preparation and isolation of polysilicon hydrides is difficult for species containing more than a few silicon atoms.〔W. W. Porterfield ''Inorganic Chemistry: A Unified Approach,'' Academic Press (1993) p. 219 ISBN 0201056607.〕 Greater catenation of the Si atoms can be obtained with the halides (Sin''X''2n+2 with n = 14 for the fluorides.〔A. Earnshaw, N. Greenwood, ''Chemistry of the Elements,'' Butterworth-Heinemnann (1997) p. 341 ISBN 0750637587.〕 Thus the polymeric silicon hydrides are formed along with smaller silicon hydride oligomers and hydrogen gas from the spontaneous but slow decomposition, as well as from the accelerated thermolysis, of acyclic and cyclic liquid silanes that are higher in molecular weight than monosilane (SiH4) and disilane (Si2H6). Polysilicon hydrides are intermediates in the high-temperature conversion of mono- and disilane to silicon and hydrogen gas. In the following idealized sequence cyclopentasilane is the polysilicon hydride intermediate: : 5 SiH4 → Si5H10 + 5 H2 :Si5H10 → 5 Si + 5H2 Polymeric silicon hydrides by be prepared by hydrolysis of certain silicides. Acid hydrolysis of calcium monosilicide (CaSi) produces (SiH2)x. CaSi consists of zigzag silicon chain with the formula (Si2−)n. This chain is preserved in the hydrolysis. This reaction was reported in 1921 by the German chemists Lothar Woehler (1870–1952) and Friedrich Mueller. In 1923, German chemists Alfred Stock (1876–1946) and Friedrich Zeidler (1855–1931) found the (SiH)x polymer is formed along with silane gas by the action of sodium amalgam on dichlorosilane (SiH2Cl2). The reaction is proposed to first produce the disodiosilane (SiH2Na2) via a Wurtz-like reaction. The SiH2Na2 dissolves in the mercury to generate the diradical SiH2, which then forms the final products.〔J. W. Mellor ''A Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. VI'' Longmans, Green and Co. (1947) pp. 970–971.〕 Polysilicon hydrides may also be produced by the dehalogenation of polysilicon halides. An illustrative reaction is the debromination of HSiBr3 with Mg in ether:〔A. F. Holleman, Egon Wiberg, Nils Wiberg, ''Inorganic Chemistry'', Academic Press (2001), pp. 844–845 ISBN 0123526515.〕 :HSiBr3 + 3/2 Mg → 1/x (SiH)x + 3/2 MgBr2 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Polysilicon hydride」の詳細全文を読む スポンサード リンク
|