Metal to ligand charge-transfer photochemistry of metal-metal bonded complexes. 5. ESR spectra of stable rhenium-. cap alpha. -diimine and spin-trapped manganese-. cap alpha. -diimine radicals
Irradiation (lambda greater than or equal to 320 nm) of (CO)/sub 5/MM'(CO)/sub 3/L and Ph/sub 3/SnM'(CO)/sub 3/L (M, M' = Mn, Re; L = ..cap alpha..-diimine = 2,2'-bipyridine, 1,10-phenanthroline, pyridine-2-carbaldehyde imine, and 1,4-diaza-1,3-butadiene) leads to homolysis of the metal-metal bond yielding fairly stable solvated radicals SM'(CO)/sub 3/L/sup ./. These paramagnetic species have been studied by ESR spectroscopy in solution directly or by using nitroso-2,2-dimethylpropane as a spin-trapping reagent. The ESR spectra show extensive hyperfine splittings of the unpaired electron with the nuclei /sup 14/N, /sup 1/H, and /sup 55/Mn or /sup 185,187/Re. From the observed and computer-simulated coupling constants important information could be derived about the electronic structure of the singly occupied molecular orbital (SOMO). After in situ addition of P(OPh)/sub 3/, P(OMe)/sub 3/, or pyridine (=L') to Re(CO)/sub 3/(t-Bu-DAB)/sup ./, the new paramagnetic adducts axial-(L')Re(CO)/sub 3/(t-Bu-DAB)/sup ./ could be identified.
- Research Organization:
- Universiteit van Amsterdam (Netherlands)
- OSTI ID:
- 7247046
- Journal Information:
- Organometallics; (United States), Vol. 7:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIPYRIDINES
ELECTRONIC STRUCTURE
PHOTOLYSIS
BUTADIENE
IMINES
MANGANESE COMPLEXES
PHENANTHROLINES
RHENIUM COMPLEXES
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
HYDROGEN 1
MANGANESE 55
NITROGEN 14
RADICALS
RHENIUM 185
RHENIUM 187
AROMATICS
AZAARENES
AZINES
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
DIENES
HEAVY NUCLEI
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MANGANESE ISOTOPES
NITROGEN ISOTOPES
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYENES
PYRIDINES
RADIOISOTOPES
RESONANCE
RHENIUM ISOTOPES
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOISOTOPES
400500* - Photochemistry