Laser flash photolysis study of photochemical carbonyl substitution in M(CO)/sub 6/ (M = Cr, Mo, W) with 1,10-phenanthroline

Journal Article · Wed Jun 01 04:00:00 EDT 1988 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00096a001· OSTI ID:6950124

Oishi, S

Photoreactions of M(CO)/sub 6/ (M = Cr, Mo, W) with 1,10-phenanthroline (phen) have been investigated by laser flash photolysis. A transient spectrum due to Cr(CO)/sub 5/(phen), where phen ligates in a monodentate fashion, was observed. In the cases of Mo and W, the growth curve of the final product, Mo(CO)/sub 4/(phen), was found to accord with the kinetics of consecutive first-order reactions. These facts indicate that, even with a ligand as well-suited to bidentate bonding as phen, the coordination of M(CO)/sub 5/ to phen does not concert with the extrusion of the second carbonyl. Both these reactions, however, were found to be significantly accelerated compared with those for pyridine derivatives, suggesting a profound electronic interaction between the metal atom and the noncoordinated nitrogen in M(CO)/sub 5/(phen). The wavelength shift of the d-d band in Cr(CO)/sub 5/(phen) is also attributable to this interaction. However, at this stage, it cannot be concluded whether the interaction is coordination, that is, whether M(CO)/sub 5/(phen) can be considered as the 7-coordinate 20-electron complex of an associative substitution mechanism.

• Research Organization: Univ. of Notre Dame, IN (USA)
• OSTI ID: 6950124
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:6; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
AROMATICS
AZAARENES
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM COMPLEXES
COMPLEXES
DATA
DECOMPOSITION
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
LASERS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENANTHROLINES
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES