Mechanism of thermal ring closure of M(CO) sub 5 L (L = bidentate ligand) produced during photolysis of group 6 hexacarbonyl complexes

Journal Article · Tue May 01 00:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00119a011· OSTI ID:6379978

Reddy, K B; van Eldik, R ^[1]

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1. 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), Vol. 9:5; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
PHOTOLYSIS
HOMOGENEOUS CATALYSIS
DATA ANALYSIS
EXPERIMENTAL DATA
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
PRESSURE DEPENDENCE
TEMPERATURE DEPENDENCE
CATALYSIS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
INFORMATION
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
400201* - Chemical & Physicochemical Properties