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Gas-phase ionization energetics, electron-transfer kinetics, and ion solvation thermochemistry of decamethylmetallocenes, chromocene, and cobaltocene

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00016a023· OSTI ID:7267259
;  [1]; ;  [2]
  1. Univ. of Florida, Gainesville, FL (United States)
  2. Univ. of Arizona, Tucson, AZ (United States)
+ Show Author Affiliations
The gas-phase free energies of ionization, [Delta]G[sub i][degrees] for Cp*[sub 2]Mn, Cp*[sub 2]Fe, Cp*[sub 2]Ni, Cp*[sub 2]Os, Cp[sub 2]Cr, and Cp[sub 2]Co (Cp = [eta][sup 5]-cyclopentadienyl, Cp[sup *] = [eta][sup 5]-pentamethylcyclopentadienyl) have been determined by using the electron-transfer equilibrium (ETE) technique and Fourier transform ion cyclotron resonance mass spectrometry. The high-resolution valence photoelectron spectra of bis(benzene)chromium(0), Bz[sub 2]Cr, Cp*[sub 2]Os, and Cp*[sub 2]Ru have also been measured. Most of the [Delta]G[sub i][degrees] values are referenced to the estimated [Delta]G[sub i][degrees] value of Bz[sub 2]Cr, for which the narrow first ionization band at 5.473 [+-] 0.005 eV is assigned as the adiabatic ionization potential. The [Delta]S[sub i][degrees] for ionization of Bz[sub 2]Cr is assumed to be equal to the electronic entropy change, [Delta]S[sub elec][degrees] (=1.4 cal mol[sup [minus]1] K[sup [minus]1]), and the difference between the integrated heat capacities for Bz[sub 2]Cr and Bz[sub 2]Cr[sup +] is also assumed to be negligible near room temperature [Delta]H[sub i,0][degrees] [approx] [Delta]H[sub i,350][degrees], leading to [Delta]G[sub i][degrees] (Bz[sub 2]-Cr) = 125.6 [+-] 1.0 kcal mol[sup [minus]1]. Through the use of thermochemical cycles, estimates are given for the average heterolytic and homolytic M-Cp bond disruption enthalpies of Cp[sub 2]Cr[sup +/0] and Cp[sub 2]Co[sup +/0]. 46 refs., 7 figs., 4 tabs.
DOE Contract Number:
FG02-86ER13501
OSTI ID:
7267259
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:4; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ALKENES
CHARGED PARTICLES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COBALT COMPLEXES
COMPILED DATA
COMPLEXES
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
ELECTRON SPECTROSCOPY
ELECTRON TRANSFER
ENERGY
ENTHALPY
ENTROPY
FOURIER TRANSFORM SPECTROMETERS
FREE ENERGY
HYDROCARBONS
INFORMATION
IONIZATION
IONS
IRON COMPLEXES
KINETICS
MANGANESE COMPLEXES
MASS SPECTROSCOPY
MEASURING INSTRUMENTS
NICKEL COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
PHOTOELECTRON SPECTROSCOPY
PHYSICAL PROPERTIES
POLYENES
REACTION KINETICS
REDOX REACTIONS
RESONANCE IONIZATION MASS SPECTROSCOPY
SOLVATION
SPECIFIC HEAT
SPECTROMETERS
SPECTROSCOPY
THERMOCHEMICAL PROCESSES
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY