Competitive hydrogen production and emission through the photochemistry of mixed-metal bimetallic complexes

Preparation of the complexes RhH{sub 2}(PPh{sub 3}){sub 2}L{sup +}, (RhH{sub 2}(PPh{sub 3}){sub 2}){sub 2}L{sup 2+}, and (bpy){sub 2}RuLRhH{sub 2}(PPh{sub 3}){sub 2}{sup 3+} where L is 2,2{prime}-bipyrimidine (bpm), 2,3-bis(2-pyridyl)pyrazine (dpp), and 2,3-bis(2-pyridyl)quinoxaline (dpq), as well a...

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Bibliographic Details
Published in:Inorganic chemistry 1990-06, Vol.29 (12), p.2313-2320
Main Authors: MacQueen, D. Brent, Petersen, John D
Format: Article
Language:English
Subjects:
08 HYDROGEN
080106 - Hydrogen- Production- Biosynthesis & Photochemical Processes
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
Exact sciences and technology
EXPERIMENTAL DATA
General and physical chemistry
HETEROCYCLIC COMPOUNDS
HYDROGEN PRODUCTION
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOSYNTHESIS
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
PYRIDINES
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
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Summary:Preparation of the complexes RhH{sub 2}(PPh{sub 3}){sub 2}L{sup +}, (RhH{sub 2}(PPh{sub 3}){sub 2}){sub 2}L{sup 2+}, and (bpy){sub 2}RuLRhH{sub 2}(PPh{sub 3}){sub 2}{sup 3+} where L is 2,2{prime}-bipyrimidine (bpm), 2,3-bis(2-pyridyl)pyrazine (dpp), and 2,3-bis(2-pyridyl)quinoxaline (dpq), as well as the monometallic analogues RhH{sub 2}(PPh{sub 3}){sub 2}en{sup +} and RhH{sub 2}(PPh{sub 3}){sub 2}bpy{sup +} (en = ethylenediamine and bpy = 2,2{prime}-bipyridine) is described. All of the complexes undergo photochemically induced reductive elimination of molecular hydrogen when irradiated at wavelengths equal to or shorter than 405 nm for the monometallic complexes and equal to or shorter than 436 nm for the bimetallic complexes. In addition, the monometallic rhodium complexes and the heterobimetallic (RuLRh) complexes under emission in fluid solution at room temperature from a state different than the photoactive state. In the case of the heterobimetallic complexes, the photoemissive state is best described as a Ru-based metal-to-ligand charge-transfer (MLCT) state while the photoreaction is assigned as a Rh-based ligand-field (LF) state in all of the complexes studied. 49 refs., 4 figs., 4 tabs.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00337a025