Activation of the C-H bonds in neopentane and neopentane-d[sub 12] by ([eta][sup 5]-C[sub 5](CH[sub 3])[sub 5])Rh(CO)[sub 2]. Spectroscopic and temporal resolution of rhodium-krypton and rhodium-alkane complex intermediates

Journal Article · Wed Oct 19 00:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00100a024· OSTI ID:6730537

Bengali, A A; Schultz, R H; Moore, C B; Bergman, R G ^[1]

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1. Lawrence Berkeley Lab., CA (United States)

The photoinitiated reaction of Cp*Rh(CO)[sub 2] with neopentane and neopentane-d[sub 12] in liquid krypton has been studied with low temperature IR flash kinetic spectroscopy. Photolysis of Cp*Rh(CO)[sub 2] generates a single transient absorption at 1946 cm[sup [minus]1] which is assigned to the Cp*Rh(CO)(Kr) complex. This complex reacts with (CH[sub 3])[sub 4]C to form the C-H activated neopentyl hydride product observed at 2008 cm[sup [minus]1]. Confirming earlier flash kinetic results with cyclohexane, the results are consistent with a pre-equilibrium mechanism in which an initially formed transient krypton complex Cp*Rh(CO)(Kr) is in rapid equilibrium with a transient (uninserted) alkane complex Cp*Rh(CO)(CH[sub 3][sub 4]C) which then proceeds to form the neopentyl hydride in a unimolecular step. Under most conditions our mechanism requires that both Cp*Rh(CO)(Kr) and Cp*Rh(CO)(alkane) exhibit unresolved carbonyl stretching absorptions at 1946 cm[sup [minus]1]. 44 refs., 7 figs., 1 tab.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6730537
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 116:21; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
2-2-DIMETHYLPROPANE
CHEMICAL BONDS
PHOTOCHEMICAL REACTIONS
CHEMICAL ACTIVATION
KRYPTON COMPLEXES
ABSORPTION SPECTRA
CHEMICAL REACTION KINETICS
RHODIUM COMPLEXES
PHOTOLYSIS
ALKANES
CARBONYLS
EQUILIBRIUM
CHEMICAL REACTIONS
COMPLEXES
DECOMPOSITION
HYDROCARBONS
KINETICS
ORGANIC COMPOUNDS
REACTION KINETICS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry