Photobehavior of copper(I) compounds. Role of copper(I)-phosphine compounds in the photosensitized valence isomerization of norbornadiene

Journal Article · Wed Jul 18 04:00:00 EDT 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00509a031· OSTI ID:5854071

Grutsch, P A; Kutal, C

The valence isomerization of norbornadiene to quadricyclene can be photosensitized with high quantum efficiency by certain copper(I)-phosphine compounds. Sensitization yields in the presence of Cu(PPh/sub 3/)/sub 2/BH/sub 4/ and Cu(PPh/sub 2/Me)/sub 3/BH/sub 4/ attain limiting values of 0.76 and 0.54, respectively, at high norbornadiene concentrations. In contrast, Cu(diphos)BH/sub 4/ (diphos is 1,2-bis(diphenylphosphino)ethane), which contains a bidentate phosphine ligand, is decidely less effective. The mechanism of sensitization by these copper(I)-phosphine compounds is fundamentally different from that exhibited by simple cuprous salts in that no ground-state coordination to the metal center occurs. A pathway involving the bimolecular interaction of the photoexcited Cu(I) compound with a ground-state norbornadiene molecule is better able to accommodate the available data. Electronic absorption and emission studies reveal some interesting differences between the spectral properties of effective vs. noneffective sensitizers.

• Research Organization: Univ. of Georgia, Athens
• OSTI ID: 5854071
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKENES
CATALYTIC EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
COPPER COMPLEXES
CYCLOALKENES
DATA
DATA FORMS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOLATED VALUES
ISOMERIZATION
NORBORNADIENE
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMISTRY
PHOTOSENSITIVITY
SENSITIVITY
TRANSITION ELEMENT COMPLEXES