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A General Pathway to Heterobimetallic Triple-Decker Complexes
Authors:Martin Piesch  Dr. Fabian Dielmann  Stephan Reichl  Prof. Dr. Manfred Scheer
Affiliation:1. Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany;2. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, 48149 Münster, Germany
Abstract:A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)2(μ,η44-C7H8)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P3, cyclo-P4, and cyclo-P5 ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η54-P5)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η33-P3)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ3541-P5){W(CO)5}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ45411-P5){(W(CO)5)2}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ3321-P3){W(CO)5}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)2(μ,η22-P2)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis.
Keywords:cobalt  cyclo-Pn ligands  iron  nickel  triple-decker complexes
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