Synthesis of tetranuclear heterometallic cluster complexes via condensation of triosmium alkyne complexes OS3(CO)10(C2R2), R = Tol and Me, and mononuclear tungsten acetylide complexes LW(CO)3C≡CR′, L = Cp and Cp*, R′ = Ph and tBu

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

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Author(s)

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

Detail(s)

Original languageEnglish
Pages (from-to)347-369
Journal / PublicationJournal of Organometallic Chemistry
Volume439
Issue number3
Publication statusPublished - 10 Nov 1992
Externally publishedYes

Abstract

Condensation of triosmium alkyne complexes OS3(CO)1O(C2R2), R = Tol and Me, with mononuclear tungsten acetylide complexes LW(CO)3C≡CR′, L = Cp and Cp*, R′ = Ph and tBu generated six WOS3 cluster complexes via 1:1 combination of the starting materials. The tetrahedral complexes LWOs3(CO)9[CC(R′)C(R)C(R)] (1) formed via coupling of the ligated alkyne with the β-carbon of the acetylide ligand were observed in all cases studied. The planar rhomboidal cluster CpWOS3(CO)1O[C(Me)C(Me)CC(Ph)] (2), generated via coupling of the ligated alkyne with the α-carbon of the acetylide ligand, was isolated only from the reaction between Os3(CO)10(C2Me2) and CpW(CO)3C≡CPh. On thermolysis, complex 2 loses one CO to afford CpWOs3(CO)10(CO)9(μ-H)[CMeC-MeCC(μ22-C6H4)] (7) via ortho-metallation of the phenyl substituent and CpWOs3(CO)9(CCMe-CMe)(μ3-CPh) (3a) via cleavage of the C-C bond of the ligated C4 hydrocarbon fragment, confirming that the alkylidyne and the coordinated C3 hydrocarbon ligands in 3a were generated via alkyne-acetylide coupling followed by cleavage of a C-C bond. For the reaction between Os3(CO)10(C2Me2) and Cp*W(CO)3C≡CPh, in addition to the expected complexes 1e and 3e (L = Cp*; R′= Ph), we observed the formation of three new complexes Cp*WOs3-(CO)9(C2Me2μ3-CCPh) (4), Cp*WOs3-(CO)9(C2Me2)(μ4-CCPh) (5) and Cp*WOs3(CO)93-CPh)[CC(Me)C(Me)CO] (6). The X-ray structural determination reveals that the butyne and acetylide ligands in butterfly complexes 4 and 5 remain as two uncoupled entities. Complexes 4 and 5 are not the precursors for the formation of other cluster complexes, as pyrolysis of these two complexes in refluxing toluene failed to afford substantial amount of butyne-acetylide coupling products. Finally, the tetrahedral complex 6 possesses two triply bridging alkylidyne ligands and a triply bridging CO ligand; the formation of alkylidyne ligands occurs via a C-C bond scission of a ligated CMeCMeCCPh fragment, except that a CO ligand inserts into the linkage between the butyne fragment and the transition metal. ...

Citation Format(s)

Synthesis of tetranuclear heterometallic cluster complexes via condensation of triosmium alkyne complexes OS3(CO)10(C2R2), R = Tol and Me, and mononuclear tungsten acetylide complexes LW(CO)3C≡CR′, L = Cp and Cp*, R′ = Ph and tBu. / Chi, Yun; Lin, Ren-Chiun; Chen, Chi-Chung; Peng, Shie-Ming; Lee, Gene-Hsiang.

In: Journal of Organometallic Chemistry, Vol. 439, No. 3, 10.11.1992, p. 347-369.

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