Synthetic applications of photosubstitution reactions of poly(pyridyl) complexes of ruthenium (II)
Two new methods for the photochemical synthesis of complexes of the type Ru(bpy)/sub 2/LX/sup +/ and Ru(bpy)/sub 2/X/sub 2/ (L = pyridine, CH/sub 3/CN, etc.; X = ClO/sub 4/, NO/sub 3/, NCS, Br, etc.) have been developed. The photochemistry is based on photosubstitution reactions of the parent complexes Ru(bpy)/sub 2/L/sub 2//sup 2 +/ most notably where L is pyridine in solvents of low polarity like dichloromethane. The photochemical methods are versatile and give products in good yield and purity. Mechanistically, the reactions appear to involve a dissociative step at the metal; a quantum yield of 0.18 is found for monosubstitution in Ru(bpy)/sub 2/(py)/sub 2//sup 2 +/, which is independent of the chemical identity and concentration of the entering ligand, X/sup -/. Some deductions about the photochemical behavior of the related complex Ru(bpy)/sub 3//sup 2 +/ based on our observations with Ru(bpy)/sub 2/L/sub 2//sup 2 +/ are also presented, and the possibility of a special medium effect in low-polarity solvents like dichloromethane is discussed.
- Research Organization:
- Univ. of North Carolina, Chapel Hill
- DOE Contract Number:
- ER-78-S-05-6034
- OSTI ID:
- 5154608
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:4; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
AZINES
BIPYRIDINES
CARBONIC ACID DERIVATIVES
CHEMICAL PREPARATION
CHEMISTRY
CHLORATES
CHLORINE COMPOUNDS
COMPLEXES
CYANIDES
DATA
DATA FORMS
ELEMENTS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HALOGENS
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOLATED VALUES
NITRATES
NITROGEN COMPOUNDS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMISTRY
PYRIDINE
PYRIDINES
RUTHENIUM COMPLEXES
SYNTHESIS
THIOCYANATES
TRANSITION ELEMENT COMPLEXES