✍ Scribed by Lothar Weber
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Phosphinidenes (phosphanylidenes) (RP) are electronically and coordinatively unsaturated phosphorus compounds, which, as six‐electron species, are formally analogous to the more familiar carbenes and nitrenes. In contrast to carbenes (CR~2~), the extremely reactive phosphinidenes cannot be isolated without decomposition. Thus, our knowledge on phosphinidenes is mainly limited to trapping reactions and quantum‐chemical calculations. There are a number of synthetic methods for phosphinidenes available, for example photolysis or thermolysis of cyclic phosphanes and oligophosphanes, dehalogenation of organodihalophosphanes, liberation of dinitrogen from organodiazidophosphanes, or decomposition of phosphoranylidene‐σ^4^‐phosphoranes (arylP=PMe~3~). A plethora of information is available on the generation of highly reactive terminal phosphinidene complexes [RPW(CO)~5~] and their chemistry. Many of these methods suffer from comparatively harsh conditions (strong base, heat, etc.) which limit their preparative use. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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