Synthesis and Characterization of Diphosphenes Bearing Fused‐Ring Bulky Rind Groups

Diphosphenes stabilized by the fused-ring bulky 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl (Rind) groups have been obtained as orange crystals by the reduction of the corresponding dichlorophosphines, (Rind)PCl2, with lithium naphthalenide (LiNaph). The molecular structures of (Eind)PCl2 and the diphosphenes, (Eind)PP(Eind) and (EMind)PP(EMind), having the bulky Eind and the less bulky EMind groups, have been confirmed by X-ray crystallography. The formation of the PP bond has been fully characterized by spectroscopic methods.