Photochemistry of (. eta. sup 5 -C sub 5 H sub 5 )Rh(CO) sub 2 in phosphine solutions: Evidence for an associative photosubstitution mechanism

Journal Article · Wed Jul 18 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00171a037· OSTI ID:6547250

Drolet, D P; Lees, A J ^[1]

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1. State Univ. of New York, Binghamton (USA)

Over the past few years there has been much interest in the photochemistry of ({eta}{sup 5}-C{sub 5}R{sub 5})ML{sub 2} and ({eta}{sup 5}-C{sub 5}R{sub 5})ML(H){sub 2} (M = Rh, Ir; R = H, CH{sub 3}; L = CO, PR{sub 3} olefin) complexes leading to intermolecular activation of hydrocarbon C-H bonds. Recently, theoretical models of methane C-H bond activation have arisen based on this premise, i.e., that a coordinatively unsaturated 16-electron ({eta}{sup 5}-C{sub 5}R{sub 5})ML complex is the key reactive intermediate. The authors present here a study of the solution photochemistry of ({eta}{sup 5}-C{sub 5}H{sub 5})Rh(CO){sub 2} in the presence of excess scavenging PPh{sub 3} ligand; the results show unequivocally that this photoreaction proceeds via an associative mechanism.

• DOE Contract Number: FG02-89ER14039
• OSTI ID: 6547250
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:15; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMISTRY
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MEASURING METHODS
NUMERICAL DATA
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMISTRY
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES