Rhodium-Catalyzed Acylation with Quinolinyl Ketones: Carbon−Carbon Single Bond Activation as the Turnover-Limiting Step of Catalysis

2011 ◽  
Vol 133 (7) ◽  
pp. 2031-2033 ◽  
Author(s):  
Colin M. Rathbun ◽  
Jeffrey B. Johnson
Keyword(s):  
Bond Activation ◽  
Single Bond ◽  
Limiting Step

Pyridine-directed carbon-carbon single bond activation: rhodium-catalyzed decarbonylation of aryl and heteroaromatic ketones

2021 ◽  
pp. 153132
Author(s):  
Cole J. Wagner ◽  
Eric A. Salisbury ◽  
Erik J. Schoonover ◽  
Jacob P. VanderRoest ◽  
Jeffrey B. Johnson
Keyword(s):  
Bond Activation ◽  
Single Bond

Iron-catalysed carbon–carbon single bond activation

2013 ◽  
Vol 11 (8) ◽  
pp. 1271 ◽  
Author(s):  
Johannes E. M. N. Klein ◽  
Bernd Plietker
Keyword(s):  
Bond Activation ◽  
Single Bond

Challenging metal-based transformations. From single-bond activation to catalysis and metallaquinonoids

2003 ◽  
Vol 75 (4) ◽  
pp. 445-460 ◽  
Author(s):  
D. Milstein
Keyword(s):  
Bond Activation ◽  
Single Step ◽  
Catalytic Reactions ◽  
Single Bond ◽  
Quinone Methides ◽  
Pd Catalysts ◽  
Biologically Relevant ◽  
Aryl Chlorides ◽  
Metal Insertion ◽  
Aluminum Alkyls

Catalytic reactions resulting from our C–X (X = H, C, O, N, halide) bond activation studies are described. Aryl chlorides can react with aluminum alkyls in preference to bromides. Using PCP-type Pd catalysts, Heck reaction with aryl iodides and bromides can proceed without involvement of Pd(0). Ru-catalyzed oxidative coupling of arenes with alkenes using O2 was accomplished. Using specifically designed systems, the scope and mechanisms of C–C activation in solution was studied and compared to C–H activation. C–C activation by Rh(I), Ir(I), Ni(II),Pt(II), Ru(II), and Os(II) was observed. Metal insertion into a strong C–C bond can be kinetically and thermodynamically more favorable than the competing C–H activation. Selective, single-step oxidative addition of a strong C–C bond to a metal was observed and kinetically evaluated. Catalytic C–C hydrogenolysis was demonstrated. A combination of C–C activation and C–R formation (R = aryl, silyl) resulted in unusual methylene transfer chemistry. Selective activation of aryl–O and Me–O bonds was observed. New types of interactions between metals and arenes and unusual quinonoid complexes, including quinone methides, xylylenes, methylene arenium, and a metallaquinone, were discovered. C–H and C–C agostic complexes of cationic metals, proposed as intermediates in bond activation, were isolated. Stabilization and controlled release of biologically relevant, extremely unstable, simple quinone methides, was accomplished.

ChemInform Abstract: Iron-Catalyzed Carbon-Carbon Single Bond Activation

ChemInform ◽  
2013 ◽  
Vol 44 (27) ◽  
pp. no-no
Author(s):  
Johannes E. M. N. Klein ◽  
Bernd Plietker
Keyword(s):  
Bond Activation ◽  
Single Bond

Twofold CC Single Bond Activation and Cleavage in the Reaction of Octatetraynes with Titanocene and Zirconocene Complexes

1997 ◽  
Vol 36 (23) ◽  
pp. 2615-2617 ◽  
Author(s):  
Paul-Michael Pellny ◽  
Normen Peulecke ◽  
Vladimir V. Burlakov ◽  
Annegret Tillack ◽  
Wolfgang Baumann ◽  
...  
Keyword(s):  
Bond Activation ◽  
Single Bond

scholarly journals Metal–ligand cooperation by aromatization–dearomatization as a tool in single bond activation

2015 ◽  
Vol 373 (2037) ◽  
pp. 20140189 ◽  
Author(s):  
David Milstein
Keyword(s):  
Bond Activation ◽  
Short Review ◽  
Catalytic Reactions ◽  
Pincer Complexes ◽  
Chemical Bonds ◽  
Single Bond ◽  
Metal Centre ◽  
Pincer Ligand ◽  
Mechanistic Insight ◽  
Metal Ligand

Metal–ligand cooperation (MLC) plays an important role in bond activation processes, enabling many chemical and biological catalytic reactions. A recent new mode of activation of chemical bonds involves ligand aromatization–dearomatization processes in pyridine-based pincer complexes in which chemical bonds are broken reversibly across the metal centre and the pincer-ligand arm, leading to new bond-making and -breaking processes, and new catalysis. In this short review, such processes are briefly exemplified in the activation of C–H, H–H, O–H, N–H and B–H bonds, and mechanistic insight is provided. This new bond activation mode has led to the development of various catalytic reactions, mainly based on alcohols and amines, and to a stepwise approach to thermal H 2 and light-induced O 2 liberation from water.

THEORETICAL INVESTIGATION ON THE ACTIVATION OF ETHANE VIA NICKEL ATOM CATALYSIS

2007 ◽  
Vol 06 (02) ◽  
pp. 323-330 ◽  
Author(s):  
LAI-CAI LI ◽  
JUN-LING LIU ◽  
JING SHANG ◽  
XIN WANG ◽  
NING-BEW WONG
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Theoretical Work ◽  
Nickel Atom ◽  
Functional Theory ◽  
Activation Pathway ◽  
Rate Determining Step ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

The reaction mechanism of the activation of ethane by nickel atom has been investigated by density functional theory (DFT). The geometries and vibration frequencies of reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311 + +G(d, p) level. Two main pathways, C – C bond activation and C – H bond activation, are identified. In former channel, the rate-limiting step is found to be hydrogen-transferring step with a high barrier of 227 kJ · mol-1. In the C – H bond activation pathway, the second hydrogen-transferring step is the rate-determining step of the whole reaction. The barrier of the step is 71 kJ · mol-1. Our results show that the studied reaction would undergo along C – H bond activation pathway to form the products H 2 molecule and Ni ⋯ethene complex. The present theoretical work indicates that Ni atom is more active than Ni + cation in activating ethane.

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