35816-56-9Relevant articles and documents
Hydride participation in electron transfer processes between metal carbonyl anions and cations
Harrigan, Marcus J.,Atwood, Jim D.
, p. 846 - 849 (2008/10/09)
Kinetic studies of selected metal carbonyl anions establish their reactivity as nucleophiles or for electron transfer. The iron species, [HFe(CO)3L]- (L = CO, PPh3), behave as metal-centered nucleophiles when reacted with [M(CO)6]+ (M = Mn, Re). Determination of the deuterium kinetic isotope ratio from kinetic studies of [HFe(CO)4]- and [DFe(CO)4]-, kH/kD = 2.8, indicates primary isotope effects for reaction with Mn(CO)6+. Initial products from transfer of a CO and back transfer of two electrons are observed in some cases. For Re-(CO)6+ exclusive formation of HRe(CO)5 as a rhenium product strongly indicates a hydrogen transfer mechanism.
Electron and bromine transfer reactions between metal carbonyl anions and metal carbonyl bromides. Crystal and molecular structure of dimeric indenyl molybdenum tricarbonyl
Striejewske, William S.,See, Ronald F.,Churchill, Melvyn Rowen,Atwood, Jim D.
, p. 4413 - 4419 (2008/10/08)
Reactions of metal carbonyl anions with metal carbonyl halides proceed by two separate paths. When the reactant anion is a strong nucleophile, the halogen is transferred, resulting in a new metal carbonyl halide and a new metal carbonyl anion as intermediates. The ultimate products, in this case, are the homobimetallic complexes. In cases where the reactant metal carbonyl anion is a poor nucleophile, a single electron transfer occurs, leading to the two homobimetallic complexes and to the heterobimetallic complex. Halide effects and possible indenyl effects are examined. The complex [Mo(indenyl)(CO)3]2 crystallizes in the noncentrosymmetric orthorhombic space group P212121 (No. 19) with a = 7.3572(7) ?, b = 14.4539(12) ?, c = 19.983(2) ?, V = 2125.0(4) ?3, and Z = 4. Diffraction data were collected on a Siemens R3m/V diffractometer for 2θ = 5-45° (Mo Kα), and the structure was solved and refined to R = 3.21% and Rw = 3.23% for all 2786 independent reflections (R = 2.26% and Rw = 2.81% for those 2314 reflections with |Fo|> 6σ(|Fo|). The complex is held together by a Mo-Mo single bond (Mo(1)-Mo(2) = 3.251(1) ?), and has Mo-CO distances ranging from 1.956(6) to 1.988(7) ?, averaging 1.970 ± 0.016 A. Molybdenum-carbon distances to the η5-indenyl rings range from 2.300(7) to 2.427(6) ? for Mo(1) and 2.306(7) to 2.430(6) ? for Mo(2).
Metal to ligand charge-transfer photochemistry of metal-metal-bonded complexes. 10. Photochemical and electrochemical study of the electron-transfer reactions of Mn(CO)3(α-diimine)(L)? (L = N-, P-Donor) radicals formed by irradiation of (CO)5MnMn(CO)3(??-diimine) complexes in the presence of L
Van Der Graaf,Hofstra,Schilder,Rijkhoff,Stufkens,Van Der Linden
, p. 3668 - 3679 (2008/10/08)
This article describes the catalytic properties of Mn(CO)3(α-diimine)(L)? radicals, formed by irradiation with visible light of the complexes (CO)5MnMn(CO)3(α-diimine) (1) in the presence of L (L = N-, P-donor). The radicals initiate the catalytic disproportionation of complexes 1 in an electron transfer chain (ETC) reaction to give Mn(CO)5- and [Mn(CO)3(α-diimine)(L)]+. The efficiency of this reaction is low if L is a hard base; it increases for ligands having smaller cone angles and, for phosphines, higher basicities. The Mn(CO)3(α-diimine)(L)? radicals also reduce several of the cluster compounds M3(CO)12-x(PR3)x (M = Fe, Ru; x = 0-2) and catalyze the substitution of CO by PR3. In that case the efficiency of the reaction is mainly determined by the reduction potentials of the [Mn(CO)3(α-diimine)(PR3)]+ cation and the cluster. These potentials have been measured with cyclic voltammetry and differential pulse voltammetry.
