581784-40-9Relevant academic research and scientific papers
P-O and C-O bond cleavages in the thermal or photochemical reactions of [Fe2( η5-C5H5)2(CO)4] with tetraethyl diphosphite
Alvarez, Celedonio M.,Galan, Belen,Garcia, M. Esther,Riera, Victor,Ruiz, Miguel A.,Bois, Claudette
, p. 3039 - 3048 (2003)
The thermal and photochemical reactions of [Fe2Cp2(CO)4] and the bidentate ligand (EtO)2POP(OEt)2 (tedip) proceed with different P-O or C-O bond cleavages in the diphosphite ligand. Thus, boiling toluene solutions of the above species yield the known compound [FeCp(CO)2{P(O)(OEt)2}] and the new dicarbonyl complexes [Fe2Cp2{μ-(EtO)2POP(O)(OEt)}{μM-P(OEt) 2}(CO)2] (three isomers). The latter are slowly decarbonylated at room temperature by atmospheric oxygen to give the metal-metal-bonded complex [Fe2Cp2{μ(EtO)2POP(O)(OEt)}{μ-P(OEt) 2}(μ-CO)]. In contrast, the photochemical reaction between the iron dimer and the diphosphite ligand gives the phosphido-phosphonate complexes [Fe2Cp2{μ-OP(OEt)2}{μ-P(OEt)2} (CO)2], as a mixture of cis and trans isomers. The latter compounds experience a remarkable P-O bond reductive elimination in boiling xylenes under a CO atmosphere, whereby the diphosphite-bridged complex [Fe2Cp2(μ-CO)2(μ-tedip)] is formed in moderate yield. The structure of the latter was analyzed through an X-ray study. The related complexes [Fe2Cp2(μ-CO)2(CO)(κ1-tedip )] and [{Fe2Cp2(μ-CO)2(CO)}2(μ-tedip) ] were prepared from [Fe2Cp2(μ-CO)2(CO)(NCMe)] and the diphosphite ligand, and their role as potential precursors of the above dicarbonyl complexes was evaluated. The structures of the new complexes are analyzed on the basis of the corresponding IR and NMR (1H, 31P, 13C) data, and the reaction pathways operative in these complex reactions are discussed on the basis of the available data and some cross-experiments.
