Highly reduced organometallics 52. Synthesis and chemistry of tricarbonylnitrosylmanganate(2−), [Mn(CO)3(NO)]2− ☆

摘要: Treatment of Mn(CO)3(NO)(PPh3) in THF at 20°C with excess sodium amalgam, followed by treatment cryptand 2.2.2, or two equiv. potassium tri-sec-butylborohydride afforded high isolated yields (≥80%) air sensitive yellow solids identified as [Na(crypt.2.2.2)]2[Mn(CO)3(NO)] and K2[Mn(CO)3(NO)], respectively. These products contain the only known mixed carbonylnitrosylmetallate dianion, isoelectronic [Fe(CO)4]2− [Mn(CO)4]3−. Reactions [Mn(CO)3(NO)]2− Ph3SnCl, Mn(CO)4(NO) Fe(CO)5, metathesis, provided new derivatives [Et4N][Mn(CO)3(NO)(SnPh3)], [PPN]2[Mn2(CO)6(NO)2], [PPN]2[MnFe(CO)7(NO)]. On basis IR spectral data latter have been formulated to non-bridged structures analogous that previously established for salt [PPN]2[Fe2(CO)8].