Electrochemical and spectroelectrochemical studies of (TPP)(Ir(CO)/sub 3/)/sub 2/) in nonaqueous media
A modified method for the synthesis of (TPP)(Ir(CO)/sub 3/)/sub 2/ from (Ir(CO)/sub 3/Cl)/sub 2/ and (TPP)H/sub 2/ where TPP is the dianion of tetraphenylporphyrin was developed and gives a much higher percent yield. Electrochemical and spectroelectrochemical studies of (TPP)(Ir(CO)/sub 3/)/sub 2/ indicate that this binuclear Ir(I) complex undergoes two reversible reductions at the porphyrin /pi/-ring system. Three irreversible oxidations are observed in benzonitrile containing 0.2 M tetrabutylammonium perchlorate, while in CH/sub 2/Cl/sub 2/, only two irreversible oxidations are recorded. The first oxidation occurs at one of the two Ir(I) centers of (TPP)(Ir(CO)/sub 3/)/sub 2/ and is followed by a rapid chemical reaction that leads to the generation of ((TPP)Ir)/sup +/ClO/sub 4//sup /minus// or a solvated form of this species in solution. An overall mechanism for the electrochemical conversion of binuclear (TPP)(Ir(CO)/sub 3/)/sub 2/ to monomeric ((TPP)Ir)/sup +/ClO/sub 4//sup /minus// and the additional reactions of this species are reported. Comparisons are also made between electrochemical properties of binuclear (TPP)(Ir(CO)/sub 3/)/sub 2/ and the binuclear Rh(I) analogue (TPP)(Rh(CO)/sub 2/)/sub 2/.
- Research Organization:
- Univ. of Houston, TX (USA)
- OSTI ID:
- 5927295
- Journal Information:
- Organometallics; (United States), Vol. 7:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPOUNDS
CHEMICAL PREPARATION
PORPHYRINS
ABSORPTION SPECTROSCOPY
CHEMICAL REACTION YIELD
ELECTROCHEMISTRY
EXPERIMENTAL DATA
OXIDATION
REDUCTION
SOLVATION
VOLTAMETRY
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
CHEMISTRY
DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
YIELDS
400400* - Electrochemistry