Synthesis and structural characterization of two novel heterometallic clusters: [Rh4Pt2(CO)11(dppm)2] and [Ru2Rh2Pt2(CO)12(dppm)2].

Two novel heterometallic octahedral clusters [Rh(4)Pt(2)(CO)(11)(dppm)(2)](1) and [Ru(2)Rh(2)Pt(2)(CO)(12)(dppm)(2)](2) were synthesized by the reaction of [Rh(2)Pt(2)(CO)(6)(dppm)(2)] with [Rh(6)(CO)(14)(NCMe)(2)] and Ru(3)(CO)(12), respectively. Solid state structures of 1 and 2 have been established by a single crystal X-ray diffraction study. Two dppm ligands in 1 are bonded to one platinum and three rhodium atoms, which form an equatorial plane of the Rh(4)Pt(2) octahedron. Two rhodium and two platinum atoms bound to the diphosphine ligands in 2 are nonplanar to give an octahedral C2 symmetric Ru(2)Rh(2)Pt(2)(dppm)2 framework. The (31)P NMR investigation of and (1D, (31)P COSY, (31)P-[(103)Rh] HMQC) and simulation of 1D spectral patterns showed that in both clusters the structures of the M(6)(PP)(2) fragments found in the solid state are maintained in solution.

[1]  Jack L. Smith,et al.  Platinum-rhodium carbonyl clusters: new structures and new types of dynamical activity. , 2004, Inorganic chemistry.

[2]  Mark D. Smith,et al.  Addition of Platinum and Palladium Tri-tert-butyl Phosphine Groups to Open Pt−Fe and Pt−Ru Metal Carbonyl Clusters , 2004 .

[3]  Mark D. Smith,et al.  Metallation of PtRu5(CO)16(μ6-C) by using bis(tri-t-butyl-phosphine) complexes of platinum and palladium , 2003 .

[4]  R. D. Adams,et al.  The Addition of Platinum and Palladium Groups to the Disulfido Ligand in Cyclopentadienyl Molybdenum-Manganese Carbonyl Complexes , 2003 .

[5]  R. D. Adams,et al.  Dynamical intramolecular metal-to-metal ligand exchange of phosphine and thioether ligands in derivatives PtRu5(CO)16(mu6-C). , 2003, Inorganic chemistry.

[6]  Mark D. Smith,et al.  Remarkable dynamical opening and closing of platinum and palladium pentaruthenium carbido carbonyl cluster complexes. , 2003, Inorganic chemistry.

[7]  T. Khimyak,et al.  Bimetallic catalysts and their relevance to the hydrogen economy , 2003 .

[8]  P. Midgley,et al.  High-performance nanocatalysts for single-step hydrogenations. , 2003, Accounts of chemical research.

[9]  P. Harvey,et al.  Bonding behavior of Co(CO)(3)L (L = CO, PPh(3)) building blocks in platinum-cobalt carbonyl clusters. , 2002, Inorganic chemistry.

[10]  M. Khalil,et al.  Ruthenium, osmium and rhodium-2,3-bis(2′-pyridyl)quinoxaline complexes , 2002 .

[11]  C. Massera,et al.  Iodo Derivatives of Bimetallic Fe—Pd and Fe—Pt Complexes. Crystal Structures of , 2001 .

[12]  G. Kickelbick,et al.  Synthesis of Co2Pt, Co2Pd and MoPd2 mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa) and (Ph2P)2NMe (dppaMe). Crystal structure of [Co2Pt(μ3-CO)(CO)6(μ-dppa)] , 1999 .

[13]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[14]  S. Tunik,et al.  MULTINUCLEAR NMR STUDIES ON SUBSTITUTED DERIVATIVES OF RH6(CO)16 IN SOLUTION , 1998 .

[15]  W. Wong,et al.  Syntheses and molecular structures of mononuclear ruthenium carbonyl complexes containing 2,1-naphthoquinone-2-oximato ligands , 1997 .

[16]  A. Poë,et al.  Associative reactions of metal carbonyl clusters: systematic kinetic studies of some ruthenium and other clusters , 1995 .

[17]  V. R. Krym,et al.  Dark and photochemical reactions of Co3Rh(Co)12 with diphenylacetylene. Crystal and molecular structure of the Co3Rh(μ2 - CO)2 (CO)8,(μ4,η2 - PhC2Ph) cluster , 1994 .

[18]  M. Garland.  Heterometallic clusters as catalyst precursors. Synergism arising from the facile generation of a reactive fragment , 1993 .

[19]  M. Wrighton,et al.  Wavelength-dependent primary photoprocesses of triosmium dodecacarbonyl in fluid solution and in rigid alkane glasses at low temperature: spectroscopic detection, characterization, and reactivity of coordinatively unsaturated triosmium undecacarbonyl , 1987 .

[20]  M. Wrighton,et al.  Wavelength-, medium-, and temperature-dependent competition between photosubstitution and photofragmentation in triruthenium dodecacarbonyl and triiron dodecacarbonyl: detection and characterization of coordinatively unsaturated trimetal undecacarbonyl complexes , 1987 .

[21]  D. Wink,et al.  Photoreactions of the triruthenium cluster Ru/sub 3/(CO)/sub 12/ and substituted analogues , 1986 .

[22]  P. Braunstein,et al.  Alkyne-substituted homo- and heterometallic carbonyl clusters of the iron, cobalt and nickel triads , 1983 .

[23]  W. E. Walker,et al.  Rhodium-carbonyl cluster chemistry under high pressure of carbon monoxide and hydrogen. 1. Infrared spectroscopic study of homogeneous systems active in the catalytic synthesis of polyalcohols from carbon monoxide and hydrogen , 1980 .

[24]  T. Hamor,et al.  Synthesis and Crystal Structure of Undecacarbonyl (triphenylphospine)-triangulo-triruthenium, Ru3(CO)11Ph3P , 1979 .