Inter-ligand azo (NN) unit formation and stabilization of a Co(ii)-diradical complex via metal-to-ligand dπ–pπ* back donation: synthesis, characterization, and theoretical study

2015 ◽  
Vol 44 (8) ◽  
pp. 3724-3727 ◽  
Author(s):  
Richa Rakshit ◽  
Samir Ghorai ◽  
Amrit Sarmah ◽  
Archana Tiwari ◽  
Ram Kinkar Roy ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Bond Formation ◽  
Unit Formation ◽  
Back Donation

Ligand H2Rich(AP)N3 provided a diradical-containing Co(ii) complex via an inter-ligand azo (NN) bond formation.

Thiolate–palladium(iv) or sulfonium–palladate(0)? A theoretical study on the mechanism of palladium-catalyzed C–S bond formation reactions

2017 ◽  
Vol 4 (6) ◽  
pp. 943-950 ◽  
Author(s):  
Dongdong Xu ◽  
Xiaotian Qi ◽  
Meng Duan ◽  
Zhaoyuan Yu ◽  
Lei Zhu ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Bond Formation ◽  
Oxidative Addition ◽  
Palladium Catalyzed ◽  
Catalytic Cycles ◽  
Bond Formation Reactions

Thiolate–palladium(iv) intermediates are generated through oxidative addition in our suggested mechanisms, and are the key intermediates in these catalytic cycles.

A New Mechanism for the First Carbon−Carbon Bond Formation in the MTG Process:  A Theoretical Study

1998 ◽  
Vol 120 (32) ◽  
pp. 8222-8229 ◽  
Author(s):  
Nobuo Tajima ◽  
Takao Tsuneda ◽  
Fuminori Toyama ◽  
Kimihiko Hirao
Keyword(s):  
Theoretical Study ◽  
Bond Formation ◽  
Carbon Bond ◽  
Carbon Carbon Bond

Synthesis, Theoretical Study and Catalytic Application of Oxidometal (Mo or V) Complexes: Unexpected Coordination Due to Ligand Rearrangement through Metal-Mediated C-C Bond Formation

2016 ◽  
Vol 2016 (10) ◽  
pp. 1604-1618 ◽  
Author(s):  
Sagarika Pasayat ◽  
Michael Böhme ◽  
Sarita Dhaka ◽  
Subhashree P. Dash ◽  
Sudarshana Majumder ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Bond Formation ◽  
Catalytic Application

scholarly journals Differences between the elimination of early and late transition metals: DFT mechanistic insights into the titanium-catalyzed synthesis of pyrroles from alkynes and diazenes

2017 ◽  
Vol 8 (3) ◽  
pp. 2413-2425 ◽  
Author(s):  
Jiandong Guo ◽  
Xi Deng ◽  
Chunyu Song ◽  
Yu Lu ◽  
Shuanglin Qu ◽  
...  
Keyword(s):  
Transition Metals ◽  
Bond Formation ◽  
Reductive Elimination ◽  
Dft Study ◽  
Late Transition Metals ◽  
Late Transition ◽  
Elimination Pathway ◽  
Back Donation

A DFT study demonstrates that titanium is capable of promoting C–N bond formation via an unconventional reductive elimination pathway featuring back-donation (REBD).

scholarly journals Activation of Acetylene by Coordination to Bis-Triphenylphosphine Complex of Pt(0): DFT Study

2009 ◽  
Vol 4 (1) ◽  
pp. 123-128
Author(s):  
N. N. Gorinchoy ◽  
B. Dobrova ◽  
M. Yu. Gorbachev ◽  
G. Munteanu ◽  
I. Ya. Ogurtsov
Keyword(s):  
Dft Calculations ◽  
Detailed Analysis ◽  
Theoretical Study ◽  
Molecular Orbitals ◽  
Dft Study ◽  
Electronic Density ◽  
Acetylene Molecule ◽  
Important Conclusion ◽  
Triphenylphosphine Complex ◽  
Back Donation

The present work is devoted to the theoretical study of the activation of the acetylene molecule coordinated in the [Pt(PPh3)2C2H2] complex. By means of DFT calculations it is shown that the geometrical and electronic characteristics of the C2H2 are essentially changed due to its coordination. The subsequent detailed analysis of the molecular orbitals (MO) of the active valence zone of this complex allows one to make important conclusion that this activation is being realized mainly due to the orbital back donation of 5d-electronic density from one of the occupied MOs of the complex [Pt(PPh3)2] to the unoccupied antibonding π*-MO of C2H2.

scholarly journals Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

2014 ◽  
Vol 10 ◽  
pp. 259-270 ◽  
Author(s):  
Shinichi Yamabe ◽  
Guixiang Zeng ◽  
Wei Guan ◽  
Shigeyoshi Sakaki
Keyword(s):  
Dft Calculations ◽  
Phenyl Ring ◽  
Theoretical Study ◽  
Bond Formation ◽  
Reduction Reaction ◽  
Base Catalyst ◽  
Reaction Channels ◽  
Catalyzed Reactions ◽  
First Time

Wolff–Kishner reduction reactions were investigated by DFT calculations for the first time. B3LYP/6-311+G(d,p) SCRF=(PCM, solvent = 1,2-ethanediol) optimizations were carried out. To investigate the role of the base catalyst, the base-free reaction was examined by the use of acetone, hydrazine (H2N–NH2) and (H2O)8. A ready reaction channel of acetone → acetone hydrazine (Me2C=N–NH2) was obtained. The channel involves two likely proton-transfer routes. However, it was found that the base-free reaction was unlikely at the N2 extrusion step from the isopropyl diimine intermediate (Me2C(H)–N=N–H). Two base-catalyzed reactions were investigated by models of the ketone, H2N–NH2 and OH−(H2O)7. Here, ketones are acetone and acetophenone. While routes of the ketone → hydrazone → diimine are similar, those from the diimines are different. From the isopropyl diimine, the N2 extrusion and the C–H bond formation takes place concomitantly. The concomitance leads to the propane product concertedly. From the (1-phenyl)ethyl substituted diimine, a carbanion intermediate is formed. The para carbon of the phenyl ring of the anion is subject to the protonation, which leads to a 3-ethylidene-1,4-cyclohexadiene intermediate. Its [1,5]-hydrogen migration gives the ethylbenzene product. For both ketone substrates, the diimines undergoing E2 reactions were found to be key intermediates.

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