Abstract
New types of triple-decker complexes with an organo-substituted P5 middle-deck were synthesized by the reaction of [Cp*Fe(η4-P5R)]- (1a: R = CH2SiMe3; 1b: R = NMe2) with halogeno-bridged transition metal dimers [Cp'''MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br). By oxidation of [(Cp*Fe)(Cp'''Co)(μ,η4:3-P5CH2SiMe3)] 2a with [Cp2Fe][PF6], the cationic complex [(Cp*Fe)(Cp'''Co)(μ,η5:4-P5CH2SiMe3)]+ was isolated. The electronic structure of the synthesized complexes was elucidated by DFT calculations.
Highlights
The reaction of 1a/1b with the transition metal dimers [Cp0 0 0MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br) leads to the tripledecker complexes 2–5, containing the whole 3d element series from Cp0 0 0Cr to Cp0 0 0Ni decks (Scheme 1)
New types of triple-decker complexes with an organo-substituted P5 middle-deck were synthesized by the reaction of [Cp*Fe(g4-P5R)]À (1a: R = CH2SiMe3; 1b: R = NMe2) with halogeno-bridged transition metal dimers [Cp0 0 0MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br)
All single-occupied molecular orbitals (SOMO) are delocalized, but the analysis of the spin density reveals that the metal centre bonded to the Cp0 0 0 ligand exhibits the highest spin density
Summary
Triple-decker sandwich complexes with a bent cyclo-P5 middle-deck† New types of triple-decker complexes with an organo-substituted P5 middle-deck were synthesized by the reaction of [Cp*Fe(g4-P5R)]À (1a: R = CH2SiMe3; 1b: R = NMe2) with halogeno-bridged transition metal dimers [Cp0 0 0MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br). The reaction of 1a/1b with the transition metal dimers [Cp0 0 0MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br) leads to the tripledecker complexes 2–5, containing the whole 3d element series from Cp0 0 0Cr to Cp0 0 0Ni decks (Scheme 1).
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