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

Journal Article · Wed Jun 13 04:00:00 EDT 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00337a025· OSTI ID:6438140

MacQueen, D B; Petersen, J D ^[1]

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1. Clemson Univ., SC (USA)

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.

• OSTI ID: 6438140
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:12; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
080106* -- Hydrogen-- Production-- Biosynthesis & Photochemical Processes
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROGEN PRODUCTION
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOSYNTHESIS
PYRIDINES
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES