(C4Me4)Co-containing triple-decker complexes with bridging heterocyclic ligands

Publication date: 1 September 2018Source: Journal of Organometallic Chemistry, Volume 870Author(s): Dmitry A. Loginov, Yulia V. Nelyubina, Alexander R. KudinovAbstract(C4Me4)Co-containing triple-decker complexes with bridging boron and phosphorus heterocyclic ligands [(C4Me4)Co(μ-η:η-L)MCp*]+ (1: M = Fe, L = C5H5BMe; 2: M = Fe, L = C4Me4P; 3a: M = Fe, L = cyclo-P5; 3b: M = Ru, L = cyclo-P5) were synthesized by photochemical reaction of [(C4Me4)Co(C6H6)]+ with sandwich compounds Cp*ML. They were isolated as salts with PF6− anion, and the structures of 1PF6, 2PF6, and 3aPF6 were determined by X-ray diffraction. The μ-pentaphospholyl complex 3a was also synthesized by exchange of sandwich compounds in the μ-cyclopentadienyl triple-decker complexes [(μ-η:η-Cp){Co(C4Me4)}2]+ or [(C4Me4)Co(μ-η:η-Cp)FeCp]+. Complexes 1, 2, and 3a undergo nucleophilic degradation by acetone and acetonitrile with selective elimination of the [(C4Me4)Co]+ fragment giving the starting sandwich compounds. The rate of the nucleophilic degradation depends on the nature of the bridging ligand and decreases in the following order: C4Me4P ≥ C5H5BMe > cyclo-P5. The bonding in 1, 2, and 3a was analyzed and compared with that in the cyclopentadienyl analog [(C4Me4)Co(μ-η:η-Cp)FeCp*]+ using energy decomposition analysis.Graphical abstract

Source: Journal of Organometallic Chemistry - July 11, 2018 Category: Chemistry Source Type: research