title: Bimetallic cluster complexes: the synthesis, structures, and bonding of ruthenium carbonyl cluster complexes containing palladium and platinum with the bulky tri-tert-butyl-phosphine ligand.
abstract: The bis-phosphine compounds M(PBut3)2, M = Pd and Pt, readily eliminate one PBut3 ligand and transfer MPBut3 groups to the ruthenium-ruthenium bonds in the compounds Ru3(CO)12, Ru6(CO)17(micro6-C), and Ru6(CO)14(eta6-C6H6)(micro6-C) without displacement of any of the ligands on the ruthenium complexes. The new compounds, Ru3(CO)12[Pd(PBut3)]3, 10, and Ru6(CO)17(micro6-C)[Pd(PBut3)]2, 11, Ru6(CO)17(micro6-C)[Pt(PBut3)]n, n = 1 (12), n = 2 (13), and Ru6(CO)14(eta6-C6H6)(micro6-C)[Pd(PBut3)]n, n = 1 (15), n = 2 (16), have been prepared and structurally characterized. In most cases the MPBut3 groups bridge a pair of mutually bonded ruthenium atoms, and the associated Ru-Ru bond distance increases in length. Fenske-Hall calculations were performed on 10 and 11 to develop an understanding of the electron deficient metal-metal bonding. 10 undergoes a Jahn-Teller distortion to increase bonding interactions between neighboring Ru(CO)4 and Pd(PBut3) fragments. 11 has seven molecular orbitals important to cluster bonding in accord with cluster electron-counting rules.
authors.affiliation: Department of Chemistry and Biochemistry and the USC NanoCenter, University of South Carolina, Columbia, South Carolina 29208 USA. adams@mail.chem.sc.edu
authors.forename: Richard D
authors.initials: RD
authors.lastname: Adams
authors.forename: Burjor
authors.initials: B
authors.lastname: Captain
authors.forename: Wei
authors.initials: W
authors.lastname: Fu
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
authors.forename: Josiah
authors.initials: J
authors.lastname: Manson
authors.forename: Mark D
authors.initials: MD
authors.lastname: Smith
authors.forename: Charles Edwin
authors.initials: CE
authors.lastname: Webster