PMID- 15962994
OWN - NLM
STAT- MEDLINE
DCOM- 20050922
LR  - 20131121
IS  - 0020-1669 (Print)
IS  - 0020-1669 (Linking)
VI  - 44
IP  - 13
DP  - 2005 Jun 27
TI  - Aqueous reductive dechlorination of chlorinated ethylenes with 
      tetrakis(4-carboxyphenyl)porphyrin cobalt.
PG  - 4852-61
AB  - The catalytic dechlorination of chlorinated ethylenes by 
      5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin cobalt ((TCPP)Co), a cobalt complex 
      structurally similar to vitamin B12, was studied. It was found to have superior 
      aqueous-phase dechlorination activity on chlorinated ethylenes (CEs) relative to 
      vitamin B12. Bimolecular rate constants for the degradation of CEs by (TCPP)Co of 
      250, 24, 0.24, and 1.5 M(-1) s(-1) were found for perchloroethylene (PCE), 
      trichloroethylene (TCE), cis-dichloroethylene (cDCE), and trans-dichloroethylene 
      (tDCE), respectively. Through kinetic analysis, the rate laws for PCE and TCE 
      were determined to be first order in substrate and catalyst, and PCE degradation 
      was shown to be sensitive to the concentration of the titanium citrate bulk 
      reductant and pH. The importance of the Co(I) oxidation state on dehalogenation 
      was studied with UV-vis absorbance spectroscopy, a variety of reducing agents, 
      and cyclic voltammetry. Evidence of chlorovinyl complexes as potential catalytic 
      cycle intermediates was obtained through the preparation of (TPP)Co(trans-C2H2Cl) 
      and the observation of (TPP)Co(C2HCl2) and (TCPP)Co(C2HCl2) by mass spectrometry. 
      The X-ray crystal structure of (TPP)Co(trans-C2H2Cl) is reported.
FAU - Fritsch, Joseph M
AU  - Fritsch JM
AD  - Department of Chemistry, University of Minnesota, 225 Pleasant Street SE, 
      Minneapolis, Minnesota 55455, USA.
FAU - McNeill, Kristopher
AU  - McNeill K
LA  - eng
PT  - Journal Article
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin cobalt)
RN  - 0 (Ethylenes)
RN  - 0 (Hydrocarbons, Chlorinated)
RN  - 0 (Metalloporphyrins)
RN  - 0 (Reducing Agents)
RN  - 0 (Water Pollutants)
RN  - 4R7X1O2820 (Chlorine)
RN  - P6YC3EG204 (Vitamin B 12)
SB  - IM
MH  - Catalysis
MH  - Chlorine/*chemistry
MH  - Crystallography, X-Ray
MH  - Electrochemistry
MH  - Ethylenes/*chemistry
MH  - Hydrocarbons, Chlorinated/*chemistry
MH  - Hydrogen-Ion Concentration
MH  - Kinetics
MH  - Metalloporphyrins/*chemical synthesis/pharmacology
MH  - Oxidation-Reduction
MH  - Reducing Agents/chemistry
MH  - Spectrophotometry, Ultraviolet
MH  - Time Factors
MH  - Vitamin B 12/*chemistry
MH  - Water Pollutants/*isolation & purification
EDAT- 2005/06/21 09:00
MHDA- 2005/09/24 09:00
CRDT- 2005/06/21 09:00
PHST- 2005/06/21 09:00 [pubmed]
PHST- 2005/09/24 09:00 [medline]
PHST- 2005/06/21 09:00 [entrez]
AID - 10.1021/ic0504339 [doi]
PST - ppublish
SO  - Inorg Chem. 2005 Jun 27;44(13):4852-61. doi: 10.1021/ic0504339.