title: The clusters [Ma(ECp*)b] (M=Pd, Pt; E=Al, Ga, In): structures, fluxionality, and ligand exchange reactions.
abstract: The synthesis and structural characterization of the novel homoleptic cluster complexes [Pd2(GaCp*)2(mu2-GaCp*)3] (1c), [Pd3(GaCp*)4(mu2-GaCp*)4] (2b) and [Pd3(AlCp*)2(mu2-AlCp*)2(mu3-AlCp*)2] (3) (Cp*=C5Me5) are presented. Furthermore, ligand exchange reactions of these cluster complexes are explored. In contrast to the electronically and sterically saturated complexes [M(ECp*)4] (M=Ni, Pd, Pt), the new unsaturated analogues [M(a)(ER)b] (E=Al, Ga, In) react with a variety of typical ligands (Cp*Al, CO, phosphines, isonitriles) to give new di- and tri-substituted compounds like [Pt2(GaCp*)2(mu2-AlCp*)3] (1d), [PdPt(GaCp*)(PPh3)(mu2-GaCp*)3] (4b), or [Pd3(PPh3)3(mu2-InCp*)(mu3-InCp*)2] (8). The trends of the reactivity of [M(a)(ER)b] as well as their fluxional behavior in solution has been elucidated by NMR spectroscopy, resulting in a mechanistic rationale for the ligand exchange reactions as well as the fluxional processes.
authors.affiliation: Anorganische Chemie II--Organometallics & Materials, Ruhr-Universität Bochum, 44780 Bochum, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Steinke
authors.forename: Christian
authors.initials: C
authors.lastname: Gemel
authors.forename: Manuela
authors.initials: M
authors.lastname: Winter
authors.forename: Roland A
authors.initials: RA
authors.lastname: Fischer