tert-Butyldichlorophosphane: crystal structure and its reactivity towards supersilyl sodium

Crystals of tBuPCl(2) were obtained by a short-path sublimation at 80 ?/0.150 mbar. The structure determination of tBuPCl2 was based on X-ray powder data. The measurements were carried out in a temperature range from 173 K to r. t. At 173 K the X-ray powder pattern has been assigned to an orthorhombic phase, and that at 213 K to a plastic-crystalline, cubic phase. We further investigated the reactivity of tBuPCl(2) towards Na(thf)(2)[SitBu(3)] at ambient temperature. The reaction of tBuPCl(2) with two equivalents of Na(thf)(2)[SitBu(3)] gave together with tBu(3)SiCl the yet unknown phosphanediide Na-2[PtBu] by a chlorine-sodium exchange. The identity of Na-2[PtBu] was confirmed by P-31 NMR spectroscopy and its existence was unambiguously demonstrated by its protonation with methanol and the consequent formation of tBuPH(2).

Automated summary

Crystals of tBuPCl(2) were obtained by short-path sublimation. The structure of tBuPCl2 was determined using X-ray powder data. The reactivity of tBuPCl(2) towards Na(thf)(2)[SitBu(3)] was investigated, resulting in the formation of a previously unknown phosphanediide Na-2[PtBu] by a chlorine-sodium exchange reaction.