Synthesis and Characterization of the Heterometallic Phosphinidene Clusters (C5Me5)WRu3(CO)103-H)(μ3-PPh), (C5H5)WRu2(CO)8(μ-H)(μ3-PPh), and (C5Me5)WRu2(CO)8(μ-H)(μ3-PPh)

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Ren-Chiun Lin
  • Yun Chi
  • Shie-Ming Peng
  • Gene-Hsiang Lee

Detail(s)

Original languageEnglish
Pages (from-to)3818-3824
Journal / PublicationInorganic Chemistry
Volume31
Issue number18
Publication statusPublished - 1 Sep 1992
Externally publishedYes

Abstract

Reaction of Ru3(CO)10(μ-H) (μ-PPh2) with an excess of tungsten hydrides LW(CO)3H, L = Cp* and Cp, in refluxing toluene produced heterometallic phosphinidene cluster complexes Cp*WRu3(CO)103-H)(μ3-PPh)(1) and CpWRu2-(CO)g(μ-H)(μ3-PPh) (2), respectively. Tetranuclear complex 1 has been identified as an intermediate to the trinuclear complex, because heating of 1 under carbon monoxide in refluxing toluene induced a cluster fragmentatio, giving an analogous phosphinidene derivative Cp*WRu2(CO)8(μ-H)(μ3-PPh) (3) in 72% yield. The structures of all three complexes were determined by X-ray diffraction. Complex 1 adopts a tetrahedral framework with a phosphinidene capping a WRU2 face and a hydride associated with the adjacent WRu2 face, whereas complexes 2 and 3 possess a triply bridging phosphinidene ligand and differ from each other by the location of the edge-bridging hydride ligand. In accordance with structural diversity in the solid state, complex 3 is present as two isomers in solution via rapid hydride migration. Crystal data for 1: space group P21/c, a = 9.813 (3) Å, b = 18.253 (4) Å, c = 18.463 (3) Å, β = 93.730 (18)°, Z = 4, final R = 0.026, Rw = 0.025 for 3750 reflections with I > (I). Crystal data for 2: space group P1, a = 9.3411 (23) Å, b = 10.2931 (14) Å, c = 12.635 (3) Å, α = 85.716 (15)°, β = 73.743 (20)°, γ = 73.013 (14)°, Z = 2, final R = 0.030, Rw = 0.035 for 3659 reflections with I > (I). Crystal data for 3: space group Cc, a = 9.711 (2) Å, b = 17.800 (3) Å, c = 32.398 (3) Å, β = 90.697 (22)°, Z = 8, final R = 0.034, Rw = 0.035 for 4487 reflections with I > (I).

Citation Format(s)

Synthesis and Characterization of the Heterometallic Phosphinidene Clusters (C5Me5)WRu3(CO)103-H)(μ3-PPh), (C5H5)WRu2(CO)8(μ-H)(μ3-PPh), and (C5Me5)WRu2(CO)8(μ-H)(μ3-PPh). / Lin, Ren-Chiun; Chi, Yun; Peng, Shie-Ming; Lee, Gene-Hsiang.

In: Inorganic Chemistry, Vol. 31, No. 18, 01.09.1992, p. 3818-3824.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review