Synthesis and derivatization of highly-functionalized λ5-phospholesElectronic supplementary information (ESI) available: Experimental details and analytical and spectroscopic data in pdf format. CCDC 929248 (4), 929250 (5) and 929251 (7). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc02089h

A variety of λ 5 -phosphole derivatives bearing up to three distinct peripheral functionalities have been prepared by regiospecific [3+2] cycloaddition reactions of the diphosphinoketenimine (PPh 2 ) 2 C&z.dbd;C&z.dbd;N t Bu ( 1 ) with electron-poor alkenes. Selective derivatization of the exocyclic functional groups, including formation of dimetallic complexes with a phosphole core, was subsequently accomplished. A variety of peripheral functionalities are present in λ 5 -phospholes prepared by regiospecific [3+2] cycloaddition reactions of diphosphinoketenimines with electron-poor alkenes.