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), Journal Name: Organometallics; (United States) Vol. 7:9; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400400* -- Electrochemistry
ABSORPTION SPECTROSCOPY
CARBOXYLIC ACIDS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELECTROCHEMISTRY
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IRIDIUM COMPOUNDS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PORPHYRINS
REDUCTION
REFRACTORY METAL COMPOUNDS
SOLVATION
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
VOLTAMETRY
YIELDS