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

We studied the electron deficient metal-metal bonding within a pair of Ruthenium complexes.

download preprint

BibTeX

@article{Adams:2004:BMC,
  author  = {Richard Adams and
             Bujor Captain and
             Wei Fu and
             Michael Hall and
             Josiah Manson and
             Mark Smith and
             Charles Webster},
  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},
  journal = {Journal of the American Chemical Society},
  year    = {2004},
  volume  = {126},
  number  = {16},
  pages   = {5253--5267},
}

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(6-C), and Ru6(CO)14(6-C6H6)(6-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(6-C)[Pd(PBut3)]2, 11, Ru6(CO)17(6-C)[Pt(PBut3)]n, n = 1 (12), n = 2 (13), and Ru6(CO)14(6-C6H6)(6-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.

License

The images, executables, and code supplied are from the web page http://josiahmanson.com. These materials are free to use for non-commercial purposes. Any works that use materials from this web page should acknowledge Josiah Manson and the paper 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. For commercial use, please contact Josiah Manson (josiahmanson@gmail.com).