Mechanism of thermal ring closure of M(CO) sub 5 L (L = bidentate ligand) produced during photolysis of group 6 hexacarbonyl complexes
- Univ. of Witten/Herdecke (West Germany)
The kinetics of the thermal ring-closure reactions of M(CO){sub 5}L, produced during the photolysis of M(CO){sub 6}/L for L = ethylenediamine (en) and 1,4-diisopropyl-1,4-diazabutadiene (dab), were studied as a function of (L), temperature, and pressure. The values of {Delta}S{double dagger} and {Delta}V{double dagger} are significantly negative, {minus}40 to {minus}170 J K{sup {minus}1} mol{sup {minus}1} and {minus}5.4 to {minus}13.7 cm{sup 3} mol{sup {minus}1}, respectively, for M = Cr (L = en) and M = Mo, W (L = en, dab) and support an associative ring-closure mechanism. The results demonstrate the crucial role played by the size of the metal center and the steric hindrance on L.
- OSTI ID:
- 6379978
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:5; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBONYLS
CATALYSIS
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
HOMOGENEOUS CATALYSIS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
TEMPERATURE DEPENDENCE
400201* -- Chemical & Physicochemical Properties
CARBONYLS
CATALYSIS
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
HOMOGENEOUS CATALYSIS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
TEMPERATURE DEPENDENCE