52542-59-3Relevant articles and documents
Highly reduced organometallics 52. Synthesis and chemistry of tricarbonylnitrosylmanganate(2-), [Mn(CO)3(NO)]2-
Chen, Yu-Sen,Ellis, John E.
, p. 675 - 682 (2008/10/08)
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.
Electron transfer between mononuclear metal carbonyl anions (M(CO)5-, M = Mn, Re; CpFe(CO)2-; CpM(CO)3-, M = Cr, Mo) and trinuclear clusters (M3(CO)12, M = Fe, Ru, Os) and between trinuclear dianions (M3(CO)112-, M = Fe, Ru, Os) and metal carbonyl dimers (Mn ...
Shauna Corraine,Atwood, Jim D.
, p. 2647 - 2651 (2008/10/08)
Full title: Electron transfer between mononuclear metal carbonyl anions (M(CO)5-, M = Mn, Re; CpFe(CO)2-; CpM(CO)3-, M = Cr, Mo) and trinuclear clusters (M3(CO)12, M = Fe, Ru, Os) and between trinuclear dianions (M3(CO)112-, M = Fe, Ru, Os) and metal carbonyl dimers (Mn2(CO)10 and Cp2M2(CO)6, M = Cr, Mo, W). Reaction of mononuclear metal carbonyl anions with trinuclear clusters of group 8 (M3(CO)12, M = Fe, Ru, Os) at ambient conditions leads to four separate outcomes: (1) formation of the metal carbonyl dimer and the trinuclear dianion which occurs whenever the two-electron reduction potential for the dimer is more negative than for the trinuclear cluster, (2) formation of MFe2(CO)7- by elimination of Fe(CO)5 which occurs for M = Re(CO)5, Mn(CO)5, and CpMo(CO)3, (3) formation of the adduct, MRu3(CO)11-, which occurs for Re(CO)5, and (4) no reaction when the two-electron reduction potential for the trinuclear complex is more negative than for the dimer. For complexes where the two-electron potential for the cluster is more negative than for the dimer, reaction of M3′(CO)112- with M2 to give M3′(CO)12 and 2M- is observed. The observed reactions allow an estimate of the two-electron reduction potentials for the trinuclear clusters. The kinetics of all of these reactions indicate a first-order dependence on the oxidant and on the reductant and are most consistent with outer-sphere electron transfer.
Steric and Electronic Factors That Control Two-Electron Processes between Metal Carbonyl Cations and Anions
Zhen, Yueqian,Feighery, William G.,Lai, Chung-Kung,Atwood, Jim D.
, p. 7832 - 7837 (2007/10/02)
Reactions of metal carbonyl cations (Mn(CO)6(+), Re(CO)6(+), Mn(CO)5PPh3(+), Mn(CO)4(PPh3)2(+), Mn(CO)5PEt3(+), Mn(CO)5PPh2Me(+), Re(CO)5PPh3(+), and CpFe(CO)3(+)) with metal carbonyl anions (Co(CO)3PPh3(-), Co(CO)4(-), Mn(CO)5(-), Mn(CO)4PPh3(-), Mn(CO)4PEt3(-), Mn(CO)4PPh2Me(-), Mn(CO)3(PPh3)2(-), CpFe(CO)2(-), Re(CO)5(-), and Re(CO)4PPh3(-)) are reported.Peak potentials are reported for all ions, and nucleophilicites (as measured by reaction with MeI) are reported for the anions.Reaction of any metal carbonyl cation with any metal carbonyl anion leads ultimately to binuclear products, which are the thermodynamic products.The binuclear products are formed by single-electron transfer.In over half of the reactions between metal carbonyl cations and anions, a two-electron change results in a new metal carbonyl cation and anion.The two-electron change may be considered mechanistically as a CO(2+) transfer with the more nucleophilic of the two anions retaining the CO(2+).The kinetic and thermodynamic driving forces and the suggested mechanism are examined.
