Molecular orbital analysis of the bonding in low nuclearity gold and platinum tertiary phosphine complexes and the development of isolobal analogies for the M(PR3) fragment

Abstract The stoichiometries and geometries of gold and platinum tertiary phosphine cluster compounds of the type M n (PR 3 ) n x + ( n = 3–6) have been analysed using extended Huckel molecular orbital calculations. The isolobal nature of the M(PH 3 ) fragment depends critically on the nature of the metal atom M, and may be used to provide a basis for predicting a wide spectrum of homo- and hetero-nuclear metal cluster compounds.

[1]  G. Sheldrick,et al.  Bridging hydrides in [H2Os3(CO)10] and [(C2H3)HOs3(CO)10]: a combined X-ray–neutron diffraction study , 1978 .

[2]  D. Mingos.  Molecular-orbital studies on carbametallaboranes. Part 1. Icosahedral carbaplatinaborane polyhedra , 1977 .

[3]  A. Stone.  New approach to bonding in transition-metal clusters and related compounds , 1981 .

[4]  R. Hoffmann,et al.  Electronic structure of M4(CO)12Hn and M4Cp4Hn complexes , 1978 .

[5]  Enrico Clementi,et al.  Simple Basis Set for Molecular Wavefunctions Containing First‐ and Second‐Row Atoms , 1964 .

[6]  D. Mingos.  Recent Developments in Theoretical Organometallic Chemistry , 1977 .

[7]  W. Lipscomb,et al.  Theory of Polyhedral Molecules. I. Physical Factorizations of the Secular Equation , 1962 .

[8]  F. Cotton,et al.  Molecular orbital calculations for complexes of heavier transition elements. I. Parameter variations in the case of tetrachloroplatinate(II) , 1967 .

[9]  R. Hoffmann.  Theoretical organometallic chemistry. , 1981, Science.

[10]  James W. White,et al.  Synthesis and X-ray structural characterization of the centred icosahedral gold cluster compound [Aul3(PMe2Ph)10Cl2](PF6)3; the realization of a theoretical prediction , 1981 .

[11]  R. Hoffmann.  An Extended Hückel Theory. I. Hydrocarbons , 1963 .

[12]  W. Nieuwpoort,et al.  APPROXIMATE RADIAL FUNCTIONS FOR FIRST-ROW TRANSITION METAL ATOMS AND IONS , 1962 .

[13]  Roald Hoffmann,et al.  Comparative bonding study of conical fragments , 1976 .

[14]  D. Mingos.  Theoretical and structural studies on organometallic cluster molecules , 1980 .

[15]  L. L. Lohr,et al.  Relativistically parameterized extended Hueckel calculations. 3. Structure and bonding for some compounds of uranium and other heavy elements , 1981 .

[16]  D. Mingos.  Molecular-orbital calculations on cluster compounds of gold , 1976 .

[17]  M. Manassero,et al.  An octahedral gold cluster: crystal and molecular structure of hexakis[tris-(p-tolyl)phosphine]-octahedro-hexagold bis(tetraphenylborate) , 1973 .

[18]  Y. Struchkov,et al.  Characteristic structural features of post-transition metal cyclopentadienyl derivatives , 1981 .

[19]  P. Raithby,et al.  Synthesis and structural characterisation of an unsaturated osmium-gold cluster HOs3Au(CO)10(PR3) (R Et, Ph); x-ray crystal structures of HOs3Au(CO)10(PPh3) and Os3Au(CO)10(PPh3)(SCN) , 1981 .

[20]  R. Hoffmann,et al.  Platinum(0)-platinum(0) dimers. Bonding relationships in a d10-d10 system , 1978 .

[21]  W. P. Bosman,et al.  Synthesis of a new heteronuclear gold–cobalt cluster. Preparation and X-ray structure determination of tetrakis (triphenylphosphine)-bis(tetracarbonylcobalt)hexagold , 1981 .

[22]  J. Ellis.  Highly Reduced Organometallics. 5. Synthesis, Properties, and the Molecular Structure of (Ph3PAu)3V(CO)5, A Gold-Vanadium Cluster , 1982 .

[23]  J. Howard,et al.  Polyhydrido-platinum clusters: synthesis and X-ray crystal structures of [Pt3H6(PBu3t)3], [Pt4H2(PBu3t)4], and [Pt4H8(PPri2Ph)4] , 1981 .

[24]  F. Cotton,et al.  Structure of triphenylphosphine-(pentahaptocyclopentadienyl)copper (I) , 1970 .

[25]  H. Hogeveen,et al.  CHEMISTRY AND SPECTROSCOPY IN STRONGLY ACIDIC SOLUTIONS .40. (CCH3)62+, AN UNUSUAL DICATION , 1974 .