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The heteronuclear cluster chemistry of the group 1B metals. Part 7. Synthesis and gold-197 Mössbauer spectra of the mixed-metal cluster compounds [Au 2 Ru 4 (µ 3 -H)(µ-H){µ-Ph 2 E(CH 2 ) n E′Ph 2 }(CO) 12 ](n= 1 or 2, E = E′= As or E = As, E′= P; n= 2, E = E′= P). X-Ray crystal structure of [Au 2 Ru 4 (µ 3 -H)(µ-H)(µ-Ph 2 AsCH 2 PPh 2 )(CO) 12 ]

1988; Royal Society of Chemistry; Issue: 7 Linguagem: Inglês

10.1039/dt9880001795

2050-5671

Scott S. D. Brown, Ian D. Salter, David B. Dyson, R. V. Parish, Paul A. Bates, Michael B. Hursthouse,

Nanocluster Synthesis and Applications

Treatment of acetone solutions of the salt [N(PPh3)2]2[Ru4(µ-H)2(CO)12] with a dichloromethane solution of the appropriate complex [Au2{µ-Ph2E(CH2)nE′Ph2}Cl2], in the presence of TlPF6, affords the mixed-metal cluster compounds [Au2Ru4(µ3-H)(µ-H){µ-Ph2E(CH2)nE′Ph2}(CO)12][E = E′= P, n= 2 (3); E = E′= As, n= 1 (4) or 2 (5); E = As, E′= P, n= 1 (6) or 2 (7)] in ca. 50–70% yield. An X-ray diffraction study on [Au2Ru4(µ3-H)(µ-H)(µ-Ph2AsCH2PPh2)(CO)12](6) revealed a metal-core structure consisting of a square-based pyramid, defined by two Au atoms and two Ru atoms in the basal plane and a Ru atom at the apex, with the Ru3 face of this Au2Ru3 unit capped by a Ru atom [Au–Au 2.832(4), Au–Ru 2.689(4)–2.846(4), and Ru–Ru 2.792(5)–3.029(5)Å]. The asymmetrical bidentate ligand bridges the two Au atoms, one hydrido ligand caps a Ru3 face and one bridges a Ru–Ru edge of the metal framework, and each Ru atom is ligated by three terminal CO groups. The 197Au Mössbauer spectra of clusters (3)–(7) are reported. These data suggest that [Au2Ru4(µ3-H)(µ-H)(µ-Ph2AsCH2AsPh2)(CO)12](4) exhibits a similar skeletal geometry to that of (6), whereas (3), (5), and (7) all adopt a capped trigonal-bipyramidal metal-core structure, with the two gold atoms occupying geometrically distinct sites.