SYNTHESIS AND REACTIVITY OF STABLE PHOSPHORUS-SUBSTITUTED NITRILIMINES - X-RAY CRYSTAL-STRUCTURE OF C-[BIS(DIISOPROPYLAMINO)THIOXOPHOSPHORANYL]-N-[BIS(DIISOPROPYLAMINO)PHOSPHANYL]NITRILIMINE

Addition of bis(diisopropylamino)chlorophosphane to the lithium salt of [bis(diisopropylamino)phosphanyl]diazomethane (6), or of diphenyl- or bis(dimethylamino)chlorophosphane to the lithium salt of [bis(diisopropylamino)thioxophosphoranyl] diazomethane (7) led to bis[[bis(diisopropylamino)]phosphanyl]diazomethane (9), [bis(diisopropylamino)-thioxophosphoranyl](diphenylphosphanyl)diazomethane (10), or [bis(diisopropylamino)thioxophosphoranyl] [bis(dimethylamino) phosphanyl]diazomethane (11), respectively. In contrast, lithium salt 7 reacted with bis(diisopropylamino)chlorophosphane or di-Zerf-butylchlorophosphane, affording C-[bis(diisopropylamino)thioxophosphoranyl]-N-[bis(diisopropylamino)phosphanyljnitrilimine (12) or C-[bis(diisopropylamino)thioxophosphoranyl]-N-[di-tret-butylphosphanyl] nitrilimine (13).In the same way, the lithium salt of (di-iert-butylthioxophosphoranyl)diazomethane (8) reacted with bis(diisopropylamino)chlorophosphane, giving C-(di-tert-butylphosphoranyl)-N-[bis(diisopropylamino)phosphanyl]nitrilimine (14). Nitrilimine 12 rearranged by heating into the isomeric diazo derivative 17, while by photolysis bis(diisopropylamino)thioxophosphoranecarbonitrile (19) and tetrakis(diisopropylamino)cyclodiphosphazene (20) were obtained. The regio- and stereoselectivity of the reactions of 12 with methyl acrylate, methyl propiolate, dimethyl fumarate, dimethyl maleate, and methyl isocyanate were studied. An X-ray diffraction study of 12, as a mixture of two enantiomers, is reported, and the geometrical parameters were compared with those predicted by theoretical calculations. © 1990, American Chemical Society. All rights reserved.