Synthesis and Platinum Complexes of an Alane‐Appended 1,1′‐Bis(phosphino)ferrocene Ligand

An aryldimethylalane‐appended analogue of 1,1′‐bis(diphenylphosphino)ferrocene, FcPPAl, was prepared, and reaction with [Pt(nb) 3 ] (nb=norbornene) afforded [Pt(η 2 ‐nb)(FcPPAl)] ( 1 ). Heating a solution of 1 to 80 °C resulted in crystallization of [{Pt(FcPPAl)} 2 ] ( 2 ), whereas treatment of 1 with C 2 H 4 , C 2 Ph 2 , H 2 , or CO provided [PtL(FcPPAl)] [L=C 2 H 4 ( 3 ), C 2 Ph 2 ( 4 )], [PtH 2 (FcPPAl)] ( 5 ), and [Pt(CO)(FcPPAl)] ( 6 ). In all complexes, the FcPPAl ligand is coordinated through both phosphines and the alane. Whereas 2 adopts a T‐shaped geometry at platinum, 3 – 5 are square‐pyramidal, and 6 is distorted square‐planar. The hydride and carbonyl complexes feature unusual multicenter bonding involving platinum, aluminum, and a hydride or carbonyl ligand.