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• W2023287445 abstract "Upon heating in toluene at reflux the di-iron heptacarbonyl complexes [Fe2(CO)6(μ-CO)(μ-R2PCH2PR2)] (RPh, Me, Et, iPr, OEt) lose carbon monoxide, resulting in phosphorus-methylene bond cleavage to give the μ- phosphidomethyl complexes [Fe2(CO)6(μ-CH2PR2)(μ-PR2)]. The ability of the phenyl group to stabilise the μ- CH2PR2 ligand is seen in the thermolyses of the diphosphine complex [Fe2(CO)6(μ-CO)(μ-Ph2PCH2PMe2)], which undergoes selective Me2PCH2 bond cleavage to yield [Fe2(CO)6(μ-CH2PPh2)(μ-PMe2)], and of the bis-diphosphine complexes [Fe2(CO)4(μ-CO)(μ-R2PCH2PR2)(μ-Ph2PCH2PPh2)] (RPh, Me), which results only in Ph2PCH2 bond cleavage to give [Fe2(CO)4(μ-R2PCH2PR2)(μ-CH2PPh2)(μ-PPh2)]. The ubiquity of μ-CH2PPh2 is attributed to the existence of a zwitterionic form in which positive charge residing on phosphorus is dispersed into the phenyl rings. The complexes [Fe2(CO)4(μ-R2PCH2PR2)(μ-CH2PPh2)(μ-PPh2)] exist as mixtures of geometric isomers a and b, identified by 31P NMR spectroscopy and an X-ray diffraction study on the major isomer a of [Fe2(CO)4(μ-Me2PCH2PMe2)(μCH2PPh2)(μ-PPh2)] as its dichloromethane solvate, which contains a cis arrangement of phosphido and phosphidomethyl ligands with the diphosphine lying trans to the latter. Methyl substitution in the diphosphine backbone suppresses phosphorus-methylene bond cleavage and results instead in ortho-metalation and phosphorus-phenyl bond cleavage. Thus, on heating [Fe2(CO)6(μ-CO){μ-Ph2PCH(Me)PPh2}] carbon monoxide and benzene are lost and [Fe2(CO)6{μ-PhPCH(Me)P(Ph)(C6H4-o)}] is formed, structurally characterised by X- ray diffraction. Substitution of two methyl groups into the diphosphine backbone favours ortho-metalation more strongly still and UV irradiation of the chelate complex [Fe(CO)3{η2-Ph2PC(Me2)PPh2}] in the presence of iron pentacarbonyl yields [Fe2(CO)6{μ-PhPC(Me2)P(Ph)(C6H4-o)}] directly. The structure of [Fe2(CO)6(μ-CO){μ-Ph2PCH(Me)PPh2}] as its hexane solvate was examined by X-ray diffraction, for comparison with that of [Fe2(CO)6(μ- CO){μ-Ph2PCH2PPh2}]. The structure analysis was not satisfactory but no significant differences between the molecular structures were observed. The suppression of backbone P-C cleavage by methyl substitution is attributed to the destabilisation of the zwitterionic form of μ-CR2PPh2, which has negative charge residing on the carbon." @default.
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• W2023287445 date "1992-08-01" @default.
• W2023287445 modified "2023-09-25" @default.
• W2023287445 title "Phosphorus-carbon bond cleavage at a di-iron centre: synthesis of μ-phosphidomethyl complexes [Fe2(CO)6(μ-CH2PR2)(μ-PR2)] from [Fe2(CO)6(μ-R2PCH2PR2)]" @default.
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• W2023287445 doi "https://doi.org/10.1016/s0020-1693(00)92368-5" @default.
• W2023287445 hasPublicationYear "1992" @default.
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