eta(5)-1,2,3-Trisilacyclopentadienyl - A Ligand for Transition Metal Complexes: Rhodium Half-Sandwich and Ruthenium Sandwich. Journal of the American Chemical Society [J Am Chem Soc] Journal article | | Title | eta(5)-1,2,3-Trisilacyclopentadienyl - A Ligand for Transition Metal Complexes: Rhodium Half-Sandwich and Ruthenium Sandwich. | | Author(s) | Yasuda H, Lee VY, Sekiguchi A | | Institution | Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. | | Source | J Am Chem Soc 2009 Jul 1. | | Abstract | The lithium salt of 1,2,3-trisilacyclopentadienide [eta(5)-((t)Bu(2)MeSi)(3)Si(3)C(2)Et(2)](-) 1(-)*[Li(+)(thf)] reacted with an equivalent amount of Rh(CO)(2)(acac) in toluene to form the half-sandwich (trisilacyclopentadienyl)dicarbonylrhodium complex [eta(5)-((t)Bu(2)MeSi)(3)Si(3)C(2)Et(2)]Rh(CO)(2) 2. pi-Electron delocalization in the trisilacyclopentadienyl ring in 2 was manifested in the shielding of the ring atoms upon complexation, as well as by the observation of (1)J(Rh-C) and (1)J(Rh-Si) coupling constants. In the solid state, cyclic delocalization in 2 was seen in the diagnostic eta(5)-coordination of the heavy cyclopentadienyl ring to the Rh center and the remarkable flattening of the Si(3)C(2) five-membered ring. Reaction of 1(-)*[Li(+)(thf)] with 0.25 equiv of [Cp*RuCl](4) (Cp* = eta(5)-C(5)Me(5)) resulted in the formation of the sandwich complex Cp*Ru[eta(5)-((t)Bu(2)MeSi)(3)Si(3)C(2)Et(2)] 3 as the heavy analogue of ruthenocene. | | Language | ENG | | Pub Type(s) | JOURNAL ARTICLE
| | PubMed ID | 19569689 |
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