Treatment of Mn(CO)3(NO)(PPh3) in THF at 20°C with excess sodium amalgam, followed by treatment with cryptand 2.2.2, or with two equiv. of potassium tri-sec-butylborohydride afforded high isolated yields (≥ 80%) of 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 with [Fe(CO)4]2- and [Mn(CO)4]3-. Reactions of [Mn(CO)3(NO)]2- with Ph3SnCl, Mn(CO)4(NO) and Fe(CO)5, followed by metathesis, provided the new derivatives [Et4N][Mn(CO)3(NO)(SnPh3)], [PPN]2[Mn2(CO)6(NO)2], and [PPN]2[MnFe(CO)7(NO)]. On the basis of IR spectral data the latter two have been formulated to contain non-bridged structures analogous to that previously established for the isoelectronic salt [PPN]2[Fe2(CO)8]. (C) 2000 Elsevier Science S.A.
Bibliographical noteFunding Information:
We sincerely thank the US National Science Foundation and the donors of the Petroleum Research Fund, administered by the American Chemical Society for financial support and Christine Lundby for her expert assistance with the manuscript. We also are indebted to Robert E. Stevens and Professor Wayne L. Gladfelter for advice on how to best prepare [Mn(CO) 4 (NO)] from readily available precursors.
- Carbonyl complexes
- Manganese complexes
- Nitrosyl complexes
- Organophosphane complexes