Improvement of the photochemical reactivity of (Cu(dmp)P2) (dmp = 2,9-dimethyl-1,10-phenanthroline; P = tertiary phosphine) by substituting PPh3 with larger phosphines: application to photoreduction of methylviologen

Journal Article · Wed Jun 03 00:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00258a036· OSTI ID:6368832

Sakaki, S; Koga, G; Hinokuma, S; Hashimoto, S; Ohkubo, K

Cu(I) complexes containing heteroaromatic ligands such as 2,2'-bipyridine (bpy) or 1,10-phenanthroline exhibit a metal-to-ligand charge-transfer (MLCT) band in the visible to near-ultraviolet spectral region and have a triplet MLCT state as the lowest energy excited state like (Ru(bpy)3)S which has been applied extensively to the photochemical reduction of water to hydrogen gas. Nevertheless, application of those Cu(I) complexes to the photochemical reduction of water has not been carried out, excepting only one report of Sauvage et al. Recently, they reported that Cu(I) complexes containing a heteroaromatic ligand, (Cu(NN)(PPh3)2) (NN = 2,9-dimethyl-1,10-phenanthroline (dmp) or 4,4',6,6'-tetramethyl-2,2'-bipyridine), found application as a sensitizer in photocatalytic reduction of methylviologen (MVS ) upon near-UV-light irradiation. Unfortunately, however, the quantum yield for MVS reduction (phi/sub MV /) is lower than that of (Ru(bpy)3)S . In this work, they have succeeded in improving the photoreducing activity of (Cu(dmp)(PPh3)S) by using such bulky and/or donating tertiary phosphines as cyclohexyldiphenylphosphine, PCyPh2, and tris(p-methoxyphenyl)phosphine, P(p-C6H4OMe)3, instead of PPh3. Another emphasis presented here lies in investigating the phosphine ligand effect on the photoreactivity of Cu(I) complexes, because such investigation has not been carried out yet to their knowledge.

• Research Organization: Kumamoto Univ., Japan
• OSTI ID: 6368832
• Journal Information: Inorg. Chem.; (United States), Vol. 26:11
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIPYRIDINES
PHOTOCHEMICAL REACTIONS
REDUCTION
COPPER COMPLEXES
CATALYTIC EFFECTS
PHENANTHROLINES
PHOSPHINES
CATALYSIS
CATALYSTS
EXPERIMENTAL DATA
PHOTOCHEMISTRY
QUANTUM EFFICIENCY
AROMATICS
AZAARENES
AZINES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
EFFICIENCY
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PYRIDINES
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry