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

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)].