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.
Solution Homolytic Bond Dissociation Energies of Organotransition-Metal Hydrides
Tilset, Mats,Parker, Vernon D.
, p. 6711 - 6717 (2007/10/02)
The homolytic bond dissociation energies (BDEs) of the mononuclear metal carbonyl hydride complexes (η5-C5H5)M(CO)3H (M = Cr, Mo, W), (η5-C5Me5)Mo(CO)3H, (η5-C5H5)W(CO)2(PMe3)H, (η5-C5H5)M(CO)2H (M = Fe, Ru), H2Fe(CO)4, Mn(CO)4PPh3H, Mn(CO)5H, Re(CO)5H, and Co(CO)3LH (L = CO, PPh3, P(OPh)3) have been estimated in acetonitrile solution by the use of a thermochemical cycle that reguires knowledge of the metal hydride pKa and the oxidation potential of its conjugate base (anion).The BDE values obtained by this method fall in the range 50-67 kcal/mol.In mostcases, these results agree well with literature data.Our data provide strong support for the common assumption that the M-H bond energies are greater for third-row and for second-row metals than for first-row metals, the difference being 5-11 kcal/mol.Effects of neither phosphine or phosphite substitution nor permethylation of the cyclopentadienyl ring on the M-H bond energies could be detected within the error limits of the method.The results are discussed in relation to previous M-H BDE estimates and metal hydride reactivity patterns.
