Phosphine and arsine derivatives of monosilane

Add time:07/24/2019    Source:sciencedirect.com

The reaction of silyl iodide with phosphorus, phosphine, arsenic and the arsenides of potassium and mercury has been studied. The compounds P(SiH3)I2 and As(SiH3)I2 have been isolated and characterized. Both decompose below 100°. Evidence is presented for the existence of the compounds P(SiH3)2I, P(SiH3)3, P(SiH3)4I, As(SiH3)2I, As(SiH3)3 and As(SiH3)4I which, however, have not yet been fully characterized. Silyl iodide forms 1:1 addition compounds with trimethylamine, triethylamine, trimethyl phosphine, triethylphosphine and trimethyl arsine. The first four are only slightly dissociated, but the arsenic compound dissociates readily. Silyl iodide also forms a compound SiH3I . 1·8 N(CH3)3 in its reaction with trimethylamine under pressure. This compound gives a non-conducting solution in acetonitrile, whereas the compounds with one mole of trimethylamine and triethylphosphine give conducting solutions and are therefore salt-like. These results are related to current theories of the formation by silicon of compounds with co-ordination number in excess of four, and of the utilization of d orbitals in bond formation.

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