(Dithiocarbamato)iron(II) complexes: Photochemical chelation and ligand exchange, comparison with electron-transfer processes, and X-ray crystal structures of Fe(. eta. sup 5 -C sub 5 Me sub 5 )(. eta. sup 1 -SC(S)NMe sub 2 )(CO) sub 2 and Fe(. eta. sup 5 -C sub 5 Me sub 5 )(. eta. sup 2 -S sub 2 CNMe sub 2 )(PPh sub 3 )
- Universite de Bordeaux I, Talence (France)
- Univ. of Texas, Austin (USA)
The X-ray crystal structure of FeCp{sup *}({eta}{sup 1}-dtc)(CO){sub 2} (1, Cp{sup *} = {eta}{sup 5}-C{sub 5}Me{sub 5}, dtc = S{sub 2}CNMe{sub 2}) confirms that the dithiocarbamate ligand is bound to iron in a monodentate mode. The photochemical chelation of 1 is carried out in dichloromethane using visible light and quantitatively gives the chelate FeCp{sup *}({eta}{sup 2}-dtc)(CO) (2) and CO. This reaction is the best route to 2 and compares with the electron-transfer chain (ETC) processes 1 {yields} 2 catalyzed by either oxidizing or reducing agents. The photolytic reaction, which can be carried out by monochromatic (330 nm) irradiation and monitored by visible spectroscopy, gives to isosbestic points at 394 and 432 nm. Both complexes 1 and 3 crystallize in a triclinic system. 1: a = 8.582 (2) {angstrom}, b = 9.046 (4) {angstrom}, c = 12.377 (7) {angstrom}, {alpha} = 97.05 (4){degree}, {beta} = 96.84 (3){degree}, {gamma} = 111.99 (3){degree}, space group P{bar 1}, Z = 2. 3: a = 11.142 (4) {angstrom}, b = 14.958 (4) {angstrom}, c = 10.382 (4) {angstrom}, {alpha} = 98.22 (2){degree}, {beta} = 115.22 (3){degree}, {gamma} 102.62 (3){degree}, space group P{bar 1}, Z = 2.
- OSTI ID:
- 6187922
- 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
CHELATING AGENTS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
IRON COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
TRANSITION ELEMENT COMPLEXES
400400* -- Electrochemistry
CHELATING AGENTS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
IRON COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
TRANSITION ELEMENT COMPLEXES