Giving Hydrides of Silicon

The first examples of the carbonylation of transition-metal complexes by carbon dioxide under mild conditions have been reported.19 For example, [RhCl(PPh3)3] reacts with C02 at room temperature in the presence of silicon hydrides to give the known [RhCl(CO)(PPh3)2], A polymeric complex has been produced from the interaction of [RhCl(CO)(PPh3)2] with a resin containing grouping (31), as part of a... 

As was the case with C/C or C/H exchange, the reactivity of silicon compounds toward catalyzed H/Cl or C/Cl exchange increases markedly when hydride groups are present on silicon. Thus, refluxing EtSiH2Cl for 15 min with chloroplatinic acid gives the conversion shown in Eq. (56) (34). 

Additions across P—H, S—H, Si—HandSn—Hbonds. Compounds with P—H bonds such as dialkyl phosphites " diphenylphosphine and tetrasubstituted phospho-ranes" react with [l.l.l]propellane, giving series of oligomers, or only monomeric products Reagents with S—H bonds (thiophenof and thiolacetic acid ) yield only monomeric products. Silicon and tin hydrides also react with neat propellanes to give monomeric products. The latter react much faster than the former. 

Silicon nitride, SigN4, is a refractory material made by direct combination of the elements above 1300°. Another method is to allow the hydrides or halides of silicon to react with ammonia and to heat the amino- and imino-silanes produced. These give the polymer [Si(NH)2] which yields SijN. ... 

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