Electron-transfer-catalyzed chelation of (Fe(. eta. sup 5 -C sub 5 R sub 5 )(. eta. sup 1 -SC(S)NMe sub 2 )(CO) sub 2 ) (R = H, Me) induced by oxidation
- Ecole Normale Superieure, Paris (France)
- Universite de Bordeaux I, Talence (France)
- Universite de Rennes I (France)
The chelation of the monodentate dithiocarbamate complexes (Fe({eta}{sup 5}-C{sub 5}R{sub 5})({eta}{sup 1}-dtc)(CO){sub 2}) (dtc = SC(S)NMe{sub 2}; R = H (1a), Me (1b)) to (Fe({eta}{sup 5}-C{sub 5}R{sub 5})({eta}{sup 2}-dtc)(CO)) (R = H (2a), Me (2b)) is catalyzed by (FeCp{sub 2}){sup +}X{sup {minus}} (X{sup {minus}} = PF{sub 6}{sup {minus}} (3a), BF{sup {minus}}{sub 4} (3b), SbCl{sup {minus}}{sub 6} (3c)) in THF. The mechanism involves the oxidation 1 + 3 {yields} 2{sup +}X{sup {minus}} + FeCp{sub 2} and the cross electron transfer (ET) 2{sup +}X{sup {minus}} + 1 {yields} 2+1{sup +}X{sup {minus}}. It shows that the deactivating step of 2b{sup +}X{sup {minus}} proceeds with a rate constant of ca. 10{sup {minus}1} s{sup {minus}1}. CV's, in the presence of PPh{sub 3}, show the existence of (FeCp{sup *}({eta}-dtc)(PPh{sub 3})){sup +/0} (4b{sup +}X{sup {minus}}/4b), and electrolysis of 1b in the presence of electrolyte gives a THF-soluble one-electron-oxidation complex, presumably (FeCp{sup *}({eta}{sup 2}-dtc)(PPh{sub 3})){sup +/0} (4b{sup +}X{sup {minus}}/4b), and electrolysis of 1b in the presence of electrolyte gives a THF-soluble one-electron-oxidation complex, presumably (FeCp{sup *}({eta}{sup 2}-dtc)(THF)){sup +}X{sup {minus}} (5b{sup +}X{sup {minus}}).
- OSTI ID:
- 6329663
- Journal Information:
- Organometallics; (USA), Vol. 9:3; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBAMATES
CHELATING AGENTS
CHEMICAL ANALYSIS
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
ORGANOMETALLIC COMPOUNDS
OXIDATION
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACID SALTS
CHEMICAL REACTIONS
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
400400* - Electrochemistry