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DOI: 10.1039/A806881J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3833-3838

Manganese(I) selenoether chemistry: synthesis, multinuclear NMR studies and the structures of [MnCl(CO)3(MeSeCH2CH2SeMe)], [MnCl(CO)3(MeSeCH2CH2CH2SeMe)] and [MnBr(CO)3{C6H4(SeMe)2-o}]

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Julie Connolly, Maxwell K. Davies and Gillian Reid

Abstract

Reaction of [Mn(CO)5X] (X = Cl, Br or I) with RSe(CH2)nSeR (R = Me or Ph, n = 2; R = Me, n = 3) or C6H4(SeMe)2-o in refluxing CHCl3 yielded the neutral manganese(II) complexes [MnX(CO)3{RSe(CH2)nSeR}] or [MnX(CO)3{C6H4(SeMe)2-o}] as yellow or orange solids. Infrared spectroscopic studies confirmed the fac-tricarbonyl arrangement. Proton, 13C-{1H}, 77Se-{1H} and 55Mn NMR spectroscopy has been used to probe the solution behaviour, and show that only those compounds involving PhSeCH2CH2SePh are undergoing rapid pyramidal inversion on the NMR timescale, with the individual NMR distinguishable invertomers observed for the other complexes (meso-1, meso-2 and DL) in varying ratios. X-Ray crystallographic analyses on three examples confirmed a fac-tricarbonyl arrangement, with the diselenoether ligand chelating: [MnCl(CO)3(MeSeCH2CH2SeMe)] and [MnCl(CO)3(MeSeCH2CH2CH2SeMe)] adopt the DL arrangement, while [MnBr(CO)3{C6H4(SeMe)2-o}] is in the meso-2 form in the solid state. These are the first structure determinations on selenoether complexes of manganese(I) carbonyl halides. Most importantly, 55Mn NMR spectroscopic studies show that δ(55Mn) is to low frequency of those of the corresponding thioether compounds, lying in the range δ –175 to –702, the lowest frequencies occurring for the iodo derivatives. The CO stretching frequencies and 55Mn NMR shifts show that, for a given X, the manganese(I) centre in [MnX(CO)3(diselenoether)] is more shielded than in [MnX(CO)3(dithioether)], possibly indicating increased σ donation in the former.

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