Dioxygen Activation by a Low-Valent Cobalt Complex Employing a Flexible Tripodal N-Heterocyclic Carbene Ligand
Hu, Xile; Castro-Rodriguez, Ingrid; Meyer, Karsten
2004

Abstract

The novel versatile Co(I) tris-carbene complex [(TIMENxyl)Co]Cl (1) (TIMEN = (tris[2-(3-aryl-2,3-dihydro-1H-imidazol-2-ylidene)ethyl]amine)) reacts with CO, 1-electron oxidizers such as CH2Cl2, and O2 to yield the Co complexes [(TIMENxyl)Co(CO)]Cl (2), [(TIMENxyl)Co(Cl)]Cl (3), and peroxo species [(TIMENxyl)Co(O2)](BPh4) (5). All new complexes were fully characterized by 1H NMR, UV/visible, and IR spectroscopy as well as superconducting quantum interference device (SQUID) magnetization measurements and single-crystal x-ray crystallog. The nucleophilic character of the eta2-bound dioxygen ligand in 5 was confirmed by d. functional theory (DFT) studies and allows for oxygen-transfer reactions with electron-deficient org. substrates, such as benzoyl chloride. [on SciFinder (R)]

Details

Title Dioxygen Activation by a Low-Valent Cobalt Complex Employing a Flexible Tripodal N-Heterocyclic Carbene Ligand
Author(s) Hu, Xile ; Castro-Rodriguez, Ingrid ; Meyer, Karsten
Published in Journal of the American Chemical Society
Volume 126
Issue 41
Pages 13464-13473
Date 2004
Keywords
Local density approximation (cobalt carbene peroxo complex; studied by; prepn.; crystal structure and reactions of cobalt carbene complexes; with/without carbonyl; chloro; acetonitrile or peroxo ligands); Carbene complexes Role: PRP; (Properties); RCT (Reactant); SPN (Synthetic preparation); PREP (Preparation); RACT (Reactant or reagent) (cobalt; prepn.; crystal structure and reactions of cobalt carbene complexes; with/without carbonyl; chloro; acetonitrile or peroxo ligands); Crystal structure; Molecular structure (of cobalt carbene complexes; with/without carbonyl; chloro; acetonitrile or peroxo ligands); Frontier molecular orbital; Magnetic moment (prepn.; crystal structure and reactions of cobalt carbene complexes; with/without carbonyl; chloro; acetonitrile or peroxo ligands); cobalt carbene complex prepn structure reaction; peroxo; cobalt carbene complex prepn structure reaction DFT; crystal; structure cobalt carbene carbonyl chloro acetonitrile peroxo; complex; mol structure cobalt carbene carbonyl chloro; acetonitrile peroxo complex
Note CAN 141:424274 29-13 Organometallic and Organometalloidal Compounds Department of Chemistry and Biochemistry,University of California San Diego,La Jolla,CA,USA. Journal 0002-7863 written in English. 794588-92-4 Role: PRP (Properties) (DFT study of structure and FMO; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-96-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (complexation with cobalt; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-99-1P; 794589-00-7P; 794589-01-8P; 794589-02-9P; 794589-05-2P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (crystal structure; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 555-77-1 (Tris(2-chloroethyl)amine); 25372-09-2 (1-(2,6-Xylyl)imidazole) Role: RCT (Reactant), RACT (Reactant or reagent) (for prepn. of carbene; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 100600-01-9P Role: SPN (Synthetic preparation), PREP (Preparation) (from benzoyl chloride and labeled peroxo complex; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 93-99-2P (Phenyl benzoate) Role: SPN (Synthetic preparation), PREP (Preparation) (from benzoyl chloride and peroxo complex; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 100-52-7P (Benzaldehyde) Role: SPN (Synthetic preparation), PREP (Preparation) (from benzylidenemalonitrile and peroxo complex; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-87-7P; 794588-89-9P; 794588-93-5P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (mol. structure; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-88-8P; 794588-91-3P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (mol. structure; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-95-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (neutralization; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 26305-75-9 (Chlorotris(triphenylphosphine)cobalt) Role: RCT (Reactant), RACT (Reactant or reagent) (prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 794588-98-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (reaction with benzoyl chloride; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands); 98-88-4 (Benzoyl chloride); 670-54-2 (Tetracyanoethylene); 2700-22-3 (Benzylidenemalonitrile) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction with peroxo complex; prepn., crystal structure and reactions of cobalt carbene complexes with/without carbonyl, chloro, acetonitrile or peroxo ligands)
DOI https://doi.org/10.1021/ja046048k
Laboratories LSCI
Record Appears in Scientific production and competences > SB - School of Basic Sciences > ISIC - Institute of Chemical Sciences and Engineering > LSCI - Laboratory of Inorganic Synthesis and Catalysis
Peer-reviewed publications
Work outside EPFL
Journal Articles
Published
Record creation date 2007-12-17

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