Mechanistic insights into a non-heme 2-oxoglutarate-dependent ethylene-forming enzyme: selectivity of ethylene-formation versusl-Arg hydroxylation

2019 ◽  
Vol 21 (19) ◽  
pp. 9957-9968 ◽  
Author(s):  
Junqin Xue ◽  
Jiarui Lu ◽  
Wenzhen Lai
Keyword(s):  
Bond Cleavage ◽  
Transition States ◽  
Ethylene Formation ◽  
Enzyme Selectivity

QM/MM calculations for a non-heme 2-oxoglutarate-dependent ethylene-forming enzyme reveal that the selectivity of ethylene formation versus succinate formation is determined by the relative energies of transition states for the competing CO2 insertion and O–O bond cleavage of the FeII-peroxysuccinate species.

Calculated Energies , Reaction Paths and Transition States of C - H Bond Cleavage in the Aromatic Molecules

2013 ◽  
Vol 8 (4) ◽  
pp. 213-224 ◽  
Author(s):  
Muthana Shanshal ◽  
Mustafa M. Muala ◽  
Muntadhar A. Alyassiri
Keyword(s):  
Bond Cleavage ◽  
Transition States ◽  
Reaction Paths ◽  
Aromatic Molecules

scholarly journals Reaction paths and transition states of the C-C and C-H bond cleavage in the aromatic anthracene and phenanthrene molecules

2016 ◽  
Vol 7 (2) ◽  
pp. 166-175 ◽  
Author(s):  
Muthana Abduljabbar Shanshal ◽  
Muntadhar Abdulbary Al-Yassiri ◽  
Qhatan Adnan Yusof
Keyword(s):  
Bond Cleavage ◽  
Transition States ◽  
Reaction Paths

Understanding the transition states of phosphodiester bond cleavage: Insights from heavy atom isotope effects

Biopolymers ◽  
2003 ◽  
Vol 73 (1) ◽  
pp. 110-129 ◽  
Author(s):  
Adam G. Cassano ◽  
Vernon E. Anderson ◽  
Michael E. Harris
Keyword(s):  
Bond Cleavage ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Transition States ◽  
Phosphodiester Bond

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.

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

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