Moessbauer spectroscopy of mixed-metal bimetallic complexes containing the pentacyanoferrate(II) metal center. [Electronic structure]
The lack of correlation of the photochemistry of the monometallic Fe(II) and Ru(II) systems with that of their bimetallic counterparts led to the studies reported. Moessbauer spectroscopy was used as a tool to assess whether d-orbital participation of the remote metal centers bound to pentacyanoferrate was responsible for the anomalous photochemical results previously observed. The complexes are listed according to descending frequency of the maximum of the Fe(II) ..-->.. L charge-transfer(MLCT) transition. The ligands are pyridine(py), CN-pyRhIII(NH/sub 3/)/sub 5/, NC-pyCoIII(CN)/sub 5/, pyrazine(pz), 4,4'-bipyridine(bpy)CoIII(CN)/sub 5/, 4,4'-bpyRhIII(NH/sub 3/)/sub 5/, pzCoIII(CN)/sub 5/, pzRhIII (NH/sub 3/)/sub 5/, and N-methylpz. Isomer shifts and quadrupole splitting are shown for both 298/sup 0/ and 77/sup 0/K spectra. The same trends are observed for the data at both temperatures. The authors concluded that the remote metal center may be treated as an electron-withdrawing substituent on the bridging ligand. Some subtle differences exist in the roles of Rh(NH/sub 3/)/sub 5//sup 3 +/ and Co(CN)/sub 5//sup 2 +/ metal centers in the back-bonding ability of L, but these factors do not explain the aforementioned discrepancies. 18 references, 1 table.
- Research Organization:
- Clemson Univ., SC
- DOE Contract Number:
- AS09-80ER10671
- OSTI ID:
- 6697488
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 22:8; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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AMMINES
AZINES
BIPYRIDINES
COBALT COMPLEXES
COMPLEXES
CORRELATIONS
CYANIDES
DATA
DATA ANALYSIS
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
GAMMA SPECTROMETERS
HETEROCYCLIC COMPOUNDS
INFORMATION
IRON COMPLEXES
LIGANDS
LOW TEMPERATURE
MEASURING INSTRUMENTS
MEDIUM TEMPERATURE
MOESSBAUER SPECTROMETERS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRAZINES
PYRIDINES
RHODIUM COMPLEXES
SPECTROMETERS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES