Photochemistry of Mo(CO) sub 6 in the gas phase

Journal Article · Thu Mar 09 00:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100342a051· OSTI ID:5115209

Ganske, J A; Rosenfeld, R N ^[1]

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1. Univ. of California, Davis (USA)

We report a study of the photochemistry of Mo(CO){sub 6} in the gas phase. Time-resolved infrared laser absorption spectroscopy is used to monitor the vibrational spectroscopy and lifetimes of the coordinatively unsaturated species formed upon photolyses at 351, 248, and 193 nm. The infrared spectra observed indicate that Mo(CO){sub 5} has C{sub 4v} symmetry, Mo(CO){sub 4} has C{sub 2v} symmetry, and Mo(CO){sub 3} has C{sub 3v} symmetry. All three unsaturated species undergo rapid association reactions with Mo(CO){sub 6} and with CO. Mo(CO){sub 5} recombines with CO with a high-pressure limiting rate constant of 2.0 ({plus minus}0.2) {times} 10{sup 6} Torr{sup {minus}1}s{sup {minus}1}. The corresponding rate constants for Mo(CO){sub 4} and Mo(CO){sub 3} are 7.5 ({plus minus}1.5) {times} 10{sup 6} and 1.8 ({plus minus}1.0) {times} 10{sup 7} Torr{sup {minus}1}s{sup {minus}1}, respectively.

• OSTI ID: 5115209
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 93:5; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
PHOTOCHEMICAL REACTIONS
MOLYBDENUM COMPOUNDS
ABSORPTION SPECTROSCOPY
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
GASES
INFRARED RADIATION
LIFETIME
PHOTOLYSIS
PRESSURE DEPENDENCE
VIBRATIONAL STATES
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ENERGY LEVELS
EXCITED STATES
FLUIDS
INFORMATION
KINETICS
NUMERICAL DATA
RADIATIONS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
400500* - Photochemistry