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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

Journal Article · · Organometallics; (USA)
DOI:https://doi.org/10.1021/om00117a017· OSTI ID:6329663
;  [1]; ;  [2];  [3]
  1. Ecole Normale Superieure, Paris (France)
  2. Universite de Bordeaux I, Talence (France)
  3. Universite de Rennes I (France)
+ Show Author Affiliations

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), Journal Name: Organometallics; (USA) Vol. 9:3; ISSN 0276-7333; ISSN ORGND
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
CARBAMATES
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACID SALTS
CHELATING AGENTS
CHEMICAL ANALYSIS
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION