Binuclear platinum(II) photochemistry. Rates of hydrogen atom transfer from organometallic hydrides to electronically excited Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/
Previous investigations have established that the triplet dsigma*psigma excited states of d/sup 8/-d/sup 8/ binuclear complexes (/sup 3/M/sub 2/*, M = Rh, Ir, Pt) are readily oxidized by one-electron acceptors. A related but largely unexplored reaction for these /sup 3/M/sub 2/* states is hydrogen atom abstraction, RH + /sup 3/M/sub 2/* ..-->.. R/sup ./ + /sup ./M/sub 2/H, a step that was proposed by Roundhill to be a primary process in the Pt/sub 2/-photocatalyzed conversion of isopropyl alcohol to acetone and dihydrogen (Pt/sub 2/ = Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/). Support for Roundhill's proposal has come from work in their laboratory that has shown that /sup 3/Pt/sub 2/* will abstract hydrogen atoms from a large number of different substrates. Because of the potential importance of H atom transfer in hydrocarbon and related small-molecule activation processes, they are engaged in studies involving systematic variations in the substrate donor to /sup 3/Pt/sub 2/*: their aim is to elucidate the factors that control the reaction rates. Here they report the results of kinetic studies of H atom transfers from organometallic hydrides to /sup 3/Pt/sub 2/*.
- Research Organization:
- California Institute of Technology, Pasadena
- OSTI ID:
- 7100905
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:1; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN TRANSFER
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PLATINUM COMPLEXES
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES