Formation of Tungsten-Triosmium Clusters. Crystal Structure and Reactivity of (η,5-C5H5)WOs3(CO)12(μ3-CC6H4CH3)(μ-H)2I

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

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Author(s)

  • Yun Chi
  • John R. Shapley
  • Melvyn Rowen Churchill
  • Yong-ji Li

Detail(s)

Original languageEnglish
Pages (from-to)4165-4170
Journal / PublicationInorganic Chemistry
Volume25
Issue number23
Publication statusPublished - 1 Nov 1986
Externally publishedYes

Abstract

Previous studies have identified three mixed-metal clusters (1-3) as the major products from the reaction of CpW(CO)2(CTol) (Cp = η5-C5H5; Tol = p-C6H4CH3) and H2Os3(CO)10. A fourth, minor, product has been isolated and identified spectroscopically as CpWOs3(CO)12(μ3-CTo1)(μ-H)2 (4). Complex 4 crystallizes in the centrosymmetric monoclinic space group 21/n with a = 12.531 (3) Å, b = 11.007 (2) Å, c = 21.733 (4)Å , ß = 105.78 (2)°, = 2884.6 (11) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4-45°) were collected on a Syntex P21, automated diffractometer, and the structure was refined to RF = 6.2% for 3014 data with |F0| > 3.0θ(|Fo|). The molecule contains a triangular triosmium core (Os(l)-Os(2) = 2.912 (1) Å, Os(2)-Os(3) = 2.875 (1) Å, Os(3)-Os(l) = 2.835 (1) Å) in which the two longer distances are believed to be associated with bridging hydride ligands; in addition, the triosmium system is capped by an asymmetrically triply bridging μ3-CTol ligand (Os(l)-C(06) = 2.184 (20) Å, Os(2)-C(06) = 2.051 (19) A, Os(3)-C(06) = 2.025 (20) A) and Os(l) is linked to a pendant CpW(CO)3 fragment (Os(l)-W = 3.097 (1) Å). In refluxing toluene complex 4 eliminates CpW(CO)3H and reacts with H2 or CO to form H3Os3(CO)9(μ3-CTol) (5) or HOs3(CO)10(μ3-CTol) (6), respectively. The related reaction of 4 with CpW(CO)2(CTol) provides CpWOs3(CO) 10(µ3- CTol)2H (3), which implicates 4 as an intermediate in the previous synthesis of 3. The reaction of CpW(CO)2(CTol) with D2Os3(CO)10 leads to a partially modified product distribution that strongly favors the acyl complex (1 -d2) at the expense of deuterated 3 + 4. This is interpreted in terms of linked pathways for forming 1 and 4 but a separate pathway for forming 2.

Citation Format(s)

Formation of Tungsten-Triosmium Clusters. Crystal Structure and Reactivity of (η,5-C5H5)WOs3(CO)12(μ3-CC6H4CH3)(μ-H)2I. / Chi, Yun; Shapley, John R.; Churchill, Melvyn Rowen; Li, Yong-ji.

In: Inorganic Chemistry, Vol. 25, No. 23, 01.11.1986, p. 4165-4170.

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