Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I)

Hevia, Eva and Miguel, Daniel and Perez, Julio and Riera, Victor (2006) Synthesis and reactivity of new (methoxy)methyl complexes of manganese(I) and rhenium(I). Organometallics, 25 (20). pp. 4909-4912. ISSN 0276-7333

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Abstract

The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) with ClCH2OCH3 afford the (methoxy) methyl complexes [M(CH2OCH3)(CO)(3)(bipy)] (M = Mn, 1; Re, 2), characterized by IR and NMR spectroscopy and, in the case of 1, also by X-ray diffraction. Highly electrophilic species, presumably cationic alkylideneoxonium complexes, although they were not detected, were prepared in situ by reaction of 1 and 2 with methyl triflate. These species react with neutral nucleophiles such as SMePh to generate the alkylidenesulfonium complexes [M(CH2SPhMe)-(CO)(3)(bipy)](+)[OTf](-) (M = Mn, 3; Re, 4) and with styrene to give phenylcyclopropane and the corresponding triflate complexes [M(OTf)(CO)(3)(bipy)].