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DOI: 10.1039/A804648D (Paper) Reference Section for: Chem. Commun., 1998, 2259-2260

Phosphorus monoxide as a quadruply bridging ligand: syntheses and X-ray crystal structures of Ru5(CO)15(µ4-PF) and [H2NCy2][Ru5(CO)15(µ4-PO)]

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John H. Yamamoto, Konstantin A. Udachin, Gary D. Enright, Arthur J. Carty and Arthur J. Carty

Abstract

The reaction of Ru4(CO)13(µ3-PNCy2) 1 with Ru(CO)5 in refluxing hexane yields Ru5(CO)15(µ4-PNCy2) 2 in high yield; treatment of 2 with HBF4·Et2O forms Ru5(CO)15(µ4-PF) 3 which is the first cluster complex to contain a µ4-fluorophosphinidene ligand, while refluxing 2 with HBF4·H2O in CH2Cl2 yields 3 and the title compound [Ru5(CO)15(µ4-P[double bond, length half m-dash]O)][H2NCy2] 4, an unprecedented example of a cluster complex containing a µ4-PO ligand.

References

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  11. Spectral data for Ru5(CO)15PF 3: IR (ν in hexane), 2068 vs, 2039 s, 2024 w, 2004 w cm–1. 31P NMR (δ in CDCl3), 548.6 (d, JP–F= 1121). 19F NMR (δ in CDCl3vs. CF3COOH), –20.49 (d, JP–F= 1121). Anal. Calc. for 3: C, 18.47, H, 0.00, N, 0.00. Found: C, 19.20, H, 0.00, N, 0.00%.
  12. Crystal data for 3: green crystals, Ru5PO15C15F, monoclinic, space group P21/n, a= 9.6072(4), b= 16.7952(7), c= 15.4589(7)Å, β= 100.65(1)°, V= 2451.4(2)Å3, Z= 4, M= 975.5 Dcalc= 2.64 mg m–3, µ= 3.15 mm–1, Mo-Kα, λ= 0.70930 Å, T= 123 K, Siemens SMART CCD, crystal size 0.27 × 0.22 × 0.09 mm, 2θmax= 57.5°, 28166 reflections measured, 6349 unique reflections, 5396 observed reflections [I > 2.5σ(I)], semi-empirical absorption correction. Structure solution by direct methods, refinement on F2 with anisotropic thermal parameters for all non-hydrogen atoms. Final R and Rw 0.033, 0.031. NRCVAX computer programs. CCDC 182/1001.
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  14. Spectral data for [Ru5(CO)15PO][H2N(Cy)2]4: IR (ν in CH2Cl2 for CO), 2061 (m), 2044(vs), 2031(m), 2013(s) cm–1. IR (ν in CH2Cl2 for PO), 1060 (m) cm–1. 1H NMR (δ in CDCl3), 6.72 (br s, 2H), 3.06 (m, 2H), 2.00 (d, 4H, JH–H= 11.30), 1.90 (d, 4H, JH–H= 11.61), 1.70 (d, 2H, JH–H= 10.63), 1.45–1.18 (m, 10H). 31P NMR (δ in CDCl3), 515. Anal. Calc. for 4: C, 28.08, H, 2.09, N, 1.21. Found: C, 27.50, H, 1.62, N, 1.52%.
  15. Crystal data for 4: green crystals, Ru5PO16C15·NC12H24, triclinic, space group P[1 with combining macron], a= 10.241(2), b= 12.914(3), c= 30.897(6)Å, α= 91.52(3), β= 99.07(3), γ= 108.18(3)°, V= 3821.4(1)Å3, Z= 4, M= 1548, Dcalc= 2.08 mg m–3, µ= 2.04 mm–1, Mo-Kα, λ= 0.70930 Å, F(000)= 2324, T= 123 K, Siemens SMART CCD, crystal size 0.04 × 0.02 × 0.15 mm, 2θmax= 57.5°, 34779 reflections measured, 19259 unique reflections, 19259 observed reflections [I > 2.5σ(I)], semiempirical absorption correction. Structure solution by direct methods, refinement on F2 with anisotropic thermal parameters for all nonhydrogen atoms. Final R and Rw 0.059, 0.093. ShelXNT computer programs. CCDC 182/1001.
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