Syntheses and Reactivity Studies of the Carbido-Alkylidyne Cluster Complexes LWRu4(μ5-C)(μ-CPh)(CO)12 and LWRu5(μ6-C)(μ-CPh)(CO)14, L = Cp and Cp*, Obtained from Reversible Scission of Acetylide Ligand

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

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Author(s)

  • Shu-Fen Hwang
  • Yun Chi
  • Shun-Jean Chiang
  • Shie-Ming Peng
  • Gene-Hsiang Lee

Detail(s)

Original languageEnglish
Pages (from-to)215-223
Journal / PublicationOrganometallics
Volume20
Issue number1
Online published7 Dec 2000
Publication statusPublished - 1 Jan 2001
Externally publishedYes

Abstract

Treatment of a 1:1 mixture of Ru3(CO)12 and the acetylide cluster LWRu2(CO)8(C2Ph) (1, L = Cp and Cp*) in hydrocarbon solvents afforded two carbido-alkylidyne cluster complexes, LWRu4(μ5-C)(CO)12(μ-CPh) (2) and LWRu5(μ6-C)(CO)14(μ-CPh) (3). Complexes 2 contain a square pyramidal cluster skeleton with a μ5-carbide and an accompanying bridging alkylidyne ligand, while WRu5 complexes 3 possess a distorted octahedral WRu5(μ6-C) framework. The transformation from 1 to 2 and 3 illustrates a reversible cleavage of an acetylide carbon−carbon bond induced by the cluster-building reaction. Moreover, the hydrogenation of complexes 2 and 3 was found to depend on the ancillary ligand on the W atom, showing selective formation of only two hydride complexes, CpWRu4(μ5-C)(μ-CPh)(μ-H)2(CO)11 (4) and Cp*WRu5(μ6-C)(μ-CPh)(μ-H)2(CO)13 (5), respectively. Single-crystal X-ray analysis on complex 4 indicated that the hydrides resided near the apical Ru atom, while the hydrides in complex 5 were associated with the unique W metal atom. Finally, treatment of 2 with thiophenol has led to formation of the wingtip-bridged butterfly complexes LWRu4(μ5-C)(μ-CPh)(μ-H)(μ-SPh)(CO)11 (7a, L = Cp; 7b, L = Cp*), in which the thiolate ligand is bonded to the Ru atoms separated by a nonbonding distance of 3.4186(8) Å.

Citation Format(s)

Syntheses and Reactivity Studies of the Carbido-Alkylidyne Cluster Complexes LWRu4(μ5-C)(μ-CPh)(CO)12 and LWRu5(μ6-C)(μ-CPh)(CO)14, L = Cp and Cp*, Obtained from Reversible Scission of Acetylide Ligand. / Hwang, Shu-Fen; Chi, Yun; Chiang, Shun-Jean; Peng, Shie-Ming; Lee, Gene-Hsiang.

In: Organometallics, Vol. 20, No. 1, 01.01.2001, p. 215-223.

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