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We report the synthesis of a niobium cyclopropyl complex, Tp(Me2)NbMe(c-C(3)H(5))(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C-H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η(2)-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C-H activation chemistry of this type represents a rather unusual reactivity pattern for η(2)-alkene complexes but is favored in this case by the strain in the C(3) ring which prevents the decomposition of the key intermediate via loss of cyclopropene.
CNRS, Laboratoire de Chimie de Coordination, 205 Route de Narbonne, F-31077 Toulouse, France.
This article was published in the following journal.
Name: Journal of the American Chemical Society
The active fragment [Tp'Rh(PMe3)], generated from a thermal precursor Tp'Rh(PMe3)(CH3)H, underwent oxidative addition of water and alcohols to give O-H adducts of the type Tp'Rh(PMe3)(OR)H (R = H, Me,...
The treatment of benzylallene-substituted internal alkynes with [RhCl(CO)2 ]2 effects a novel cycloisomerization by C(sp(2) )-H bond activation to produce hexahydrophenanthrene derivatives. The reacti...
The first C-H bond functionalization with amides as the coupling partners via selective activation of the amide N-C bond using rhodium(I) catalysts under highly chemoselective conditions is reported. ...
Geometries of benzene complexes with C6F5X, C6H5X and CF3X (X is I, Br, Cl, F) were optimized and their interaction energies were evaluated. The CCSD(T) interaction energies at the basis set limit (Ei...
Generation of ortho-SF5-benzyne was achieved by a lithiation/elimination sequence starting from 2-fluoro-SF5-benzene. The highly reactive ortho-SF5-benzyne intermediate was trapped by furan or 2-methy...
The research is to evaluate benzene metabolism after exposure at levels that can be found in the environment, such as the higher end concentrations in the air inside cars and buses while b...
The purpose of this study is to investigate the health effects of benzene exposure in workers in Shanghai, China.
This study compares air pollution exposures of residents in a South Baltimore community next to major industry with those in a comparison community with much less industry nearby. Parents ...
RATIONALE: Exposure to low-level benzene in the work place may affect the risk of developing cancer later in life. Learning about the long-term effects of benzene exposure may help the stu...
The Veterans Health Administration (VHA) has stated the need for a brief screening instrument that can assist with the triage of the enormous number of returning OEF/OIF veterans with conc...
Niobium. A metal element atomic number 41, atomic weight 92.906, symbol Nb. (From Dorland, 28th ed)
Complexes of enzymes that catalyze the covalent attachment of UBIQUITIN to other proteins by forming a peptide bond between the C-terminal GLYCINE of UBIQUITIN and the alpha-amino groups of LYSINE residues in the protein. The complexes play an important role in mediating the selective-degradation of short-lived and abnormal proteins. The complex of enzymes can be broken down into three components that involve activation of ubiquitin (UBIQUITIN-ACTIVATING ENZYMES), conjugation of ubiquitin to the ligase complex (UBIQUITIN-CONJUGATING ENZYMES), and ligation of ubiquitin to the substrate protein (UBIQUITIN-PROTEIN LIGASES).
The sequential activation of serum COMPLEMENT PROTEINS to create the COMPLEMENT MEMBRANE ATTACK COMPLEX. Factors initiating complement activation include ANTIGEN-ANTIBODY COMPLEXES, microbial ANTIGENS, or cell surface POLYSACCHARIDES.
UNSATURATED FATTY ACIDS that contain at least one double bond in the trans configuration, which results in a greater bond angle than the cis configuration. This results in a more extended fatty acid chain similar to SATURATED FATTY ACIDS, with closer packing and reduced fluidity. HYDROGENATION of unsaturated fatty acids increases the trans content.
Unsaturated derivatives of the steroid androstane containing at least one double bond at any site in any of the rings.