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gamma. and pulse radiolysis study of the reactions of hydrido complexes of iron(II) containing organonitriles in methanol

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100459a029· OSTI ID:6861527
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In methanolic solution deaerated with argon, the complexes of general formula t-FeH(L)(DPE)/sub 2/+, where DPE = 1,2-bis(diphenylphosphine)ethane and L = CH/sub 3/CN, CH/sub 3/CH/sub 2/CN, CH/sub 2/CHCN, C/sub 6/H/sub 5/CN, and p-CH/sub 3/C/sub 6/H/sub 4/CN, are reduced to FeH(L)(DPE)/sub 2/ by solvated electrons. For the reaction FeH(L)(DPE)/sub 2/+ + e/sub 8/-..-->.. FeH(L)(DPE)/sub 2/, k = (2.8 +- 0.3) x 10/sup 10/ M/sup -1/ s/sup -1/ for all of the compounds. With FeH(CH/sub 2/CHCN)(DPE)/sub 2/+ only, a reaction with the radical CH/sub 2/OH has also been observed. This reaction, which is supposed to proceed via addition of the radical to the coordinated CH/sub 2/CHCN, leads to the saturation of the double bond. When L = CH/sub 3/CN, CH/sub 3/CH/sub 2/CN, C/sub 6/H/sub 5/CN, and p-CH/sub 3/C/sub 6/H/sub 4/CN, FeH(L)(DPE)/sub 2/ rearranges, losing the ligand L to give the already known iron(I) complex, FeH(DPE)/sub 2/, which in methanol has a t/sub 1/2/ greater than or equal to 1 s. The rate constants for this process have been determined. The complex FeH(p-ClC/sub 6/H/sub 4/Cn)(DPE)/sub 2/+ on reacting with e/sub 8//sup -/ undergoes the detachment of Cl/sup -/ from the ligand, while the radical intermediate FeH(C/sub 6/H/sub 4/CN)(DPE)/sub 2/+ reacts rapidly with the solvent to give the complex FeH(C/sub 6/H/sub 5/N)(DPE)/sub 2/+ as final product.

Research Organization:
Consiglio Nazionale delle Ricerche, Padua, Italy
OSTI ID:
6861527
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84:22; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALCOHOLS
ARGON
AROMATICS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED AROMATIC HYDROCARBONS
COMPARATIVE EVALUATIONS
COMPLEXES
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
FLUIDS
GAMMA RADIATION
GASES
HALOGENATED AROMATIC HYDROCARBONS
HYDROXY COMPOUNDS
IONIZING RADIATIONS
IRON COMPLEXES
IRRADIATION
KINETICS
LEPTONS
LIGANDS
METHANOL
NITRILES
NONMETALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS
RARE GASES
REACTION KINETICS
SOLVATED ELECTRONS
TRANSITION ELEMENT COMPLEXES