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The reaction of cyclodimeric group 4b metallocene sulfides [(RCp) 2 MS] 2  (M = Zr, R = H, Me, tBu: 2a-c; M = Hf, R = H, Me: 2d,e) with trialkylaluminum compounds gives dimeric sulfur-bridged metallocene/aluminum complexes [(RCp) 2 M(R′)SAlR′ 2 ] 2  (M = Zr, R = H, Me, tBu, R′ = Me: 3a-c; M = Hf, R = H, Me, R′ = Me: 3d,e, R′ = Et: 3f,g). At low temperature the primarily formed adduct [(MeCp) 2 ZrS] 2  · AlMe 3  6 was isolated and its temperature-de-pendent dynamic NMR spectra monitored. The metallocene sulfide/trialkylaluminum addition products exhibit a reaction pattern which indicates the occurrence of reversible alkyl migration between the main group and transition metal center. This may be of relevance for developing novel types of olefin oligomerization catalysts.

zeitschrift für naturforschung b

Schwefelverbrückte Metallocen/Aluminium-Verbindungen - Isolierung und dynamisches Verhalten von [(MeCp) 2 ZrS] 2  · AlMe 3  / Sulfur-Bridged Metallocene/Aluminum Complexes - Isolation and Dynamic Behaviour of [(MeCp) 2 ZrS] 2  · AlMe 3