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(η2‐nb)(FcPPAl)] (1). Heating a solution of 1 to 80 °C resulted in crystallization of [{Pt(FcPPAl)}2] (2), whereas treatment of 1 with C2H4, C2Ph2, H2, or CO provided [PtL(FcPPAl)] [L=C2H4 (3), C2Ph2 (4)], [PtH2(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. [{Pt(FcPPAl}2], [PtLx(FcPPAl)] (Lx=norbornene(nb), C2H4, C2Ph2, and H2), and [Pt(CO)(FcPPAl)] featuring T‐shaped, square‐pyramidal, and distorted square‐planar geometries were synthesized from an alane‐appended bis(phosphino)ferrocene ligand, FcPPAl. In all cases, the FcPPAl ligand coordinates through both phosphine donors and the alane, and the hydride and carbonyl complexes feature unusual multicenter bonding involving Pt, Al, and an H or CO ligand.