Oligosilyl Substituted Phosphanes and Arsanes

The project envisages the synthesis of phosphanes and arsanes RE(SiMe3)2 (E = P, As, R = oligosilyl such as Si(SiMe3)3). By reaction with hexachloroethane, the halogenated compounds RECl(SiMe3) will be synthesized, which in turn will be treated with tertBuOK giving phosphinidenes and arsinidenes RP and RAs, besides KG and tertBuOSiMe3. Reactions of these short-lived intermediates giving double-bonded species such as di(oligosilyl)diphosphenes and di(oligosilyl)diarsenes, or depending an the reaction conditions di(oligosilyl)triphosphaallyl anions and di(oligosilyl)hiarsaallyl anions will be studied. By synthesis of oligosilanes bearing two bis(trimethylsilyl)phosphino- or arsino groups, cyclic or polymeric compounds with P=P or As=As double bonds will be prepared using the reaction sequence described above. The reaction of di(oligosilyl)chlorophosphanes and di(oligosilyl)chloroarsanes with tertBuOK is expected to result in the simultaneous generation of a silylene and a phosphinidene (or an arsinidene). Their reactions will be studied. The properties of the target molecules will be studied by NMR spectroscopy, X-ray crystallography, vibrational spectroscopy and ab initio calculations.