Mechanistic Insights into the C–H Bond Activation of Hydrocarbons by Chromium(IV) Oxo and Chromium(III) Superoxo Complexes

2013 ◽  
Vol 53 (1) ◽  
pp. 645-652 ◽  
Author(s):  
Kyung-Bin Cho ◽  
Hyeona Kang ◽  
Jaeyoung Woo ◽  
Young Jun Park ◽  
Mi Sook Seo ◽  
...  
Keyword(s):  
Bond Activation ◽  
Activation Of Hydrocarbons

scholarly journals C−H Bond Activation of Hydrocarbons by an Imidozirconocene Complex

2004 ◽  
Vol 126 (4) ◽  
pp. 1018-1019 ◽  
Author(s):  
Helen M. Hoyt ◽  
Forrest E. Michael ◽  
Robert G. Bergman
Keyword(s):  
Bond Activation ◽  
Activation Of Hydrocarbons

A New Pathway for Activation of C - C and C - H Bonds by Transition Metals in the Gas Phase

2005 ◽  
Vol 58 (2) ◽  
pp. 82 ◽  
Author(s):  
Dongju Zhang ◽  
Ruoxi Wang ◽  
Rongxiu Zhu
Keyword(s):  
Transition Metals ◽  
Gas Phase ◽  
Density Functional Calculations ◽  
Density Functional ◽  
Bond Activation ◽  
Level Density ◽  
Elimination Mechanism ◽  
Activation Of Hydrocarbons ◽  
High Level ◽  
H2 Elimination

C–H and C–C bond activation of hydrocarbons at metal centres are of fundamental importance in biochemistry, organometallic chemistry, and catalysis. The present work aims to search for novel mechanisms for activation of C–C and C–H bonds by transition metals in the gas phase. Using high-level density functional calculations, we systemically studied the reactions of Ti+, V+, and Fe+ with ethane, and proposed new pathways of C–C and C–H bond activation—concerted activation of C–C and C–H bonds, and 1,2-H2 elimination. These two pathways clearly differ from the general addition–elimination mechanism.

scholarly journals C—H Bond Activation of Hydrocarbons by an Imidozirconocene Complex.

ChemInform ◽  
2004 ◽  
Vol 35 (23) ◽  
Author(s):  
Helen M. Hoyt ◽  
Forrest E. Michael ◽  
Robert G. Bergman
Keyword(s):  
Bond Activation ◽  
Activation Of Hydrocarbons

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Imine as a Linchpin Approach for Distal C(sp2)–H Functionalization

2020 ◽  
Author(s):  
Sukdev Bag ◽  
Sadhan Jana ◽  
Sukumar Pradhan ◽  
Suman Bhowmick ◽  
Nupur Goswami ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Bond Activation ◽  
Bond Formation ◽  
Ancillary Ligand ◽  
Significant Challenge ◽  
Site Selectivity ◽  
Directing Group ◽  
Covalently Linked ◽  
Complex Organic ◽  
Post Functionalization

<p>Despite the widespread applications of C–H functionalization, controlling site selectivity remains a significant challenge. Covalently attached directing group (DG) served as an ancillary ligand to ensure proximal <i>ortho</i>-, distal <i>meta</i>- and <i>para</i>-C-H functionalization over the last two decades. These covalently linked DGs necessitate two extra steps for a single C–H functionalization: introduction of DG prior to C–H activation and removal of DG post-functionalization. We introduce here a transient directing group for distal C(<i>sp<sup>2</sup></i>)-H functionalization <i>via</i> reversible imine formation. By overruling facile proximal C-H bond activation by imine-<i>N</i> atom, a suitably designed pyrimidine-based transient directing group (TDG) successfully delivered selective distal C-C bond formation. Application of this transient directing group strategy for streamlining the synthesis of complex organic molecules without any necessary pre-functionalization at the distal position has been explored.</p>

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