Aryl-F Bond Cleavage vs. C-E Reductive Elimination: Competitive Pathways of Metal-Ligand-Cooperation-Based E-H Bond Activation (E = N, S)

2015 ◽  
Vol 2015 (28) ◽  
pp. 4761-4768 ◽  
Author(s):  
Adam Scharf ◽  
Israel Goldberg ◽  
Arkadi Vigalok ◽  
Andrei N. Vedernikov
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Reductive Elimination ◽  
Metal Ligand

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.

scholarly journals The Exchange of Cyclometalated Ligands

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 210
Author(s):  
Alexander D. Ryabov
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Cyclopalladated Complexes ◽  
Derivatives Of ◽  
Cyclometalated Ligand ◽  
Incoming Ligand

Reactions of cyclometalated compounds are numerous. This account is focused on one of such reactions, the exchange of cyclometalated ligands, a reaction between a cyclometalated compound and an incoming ligand that replaces a previously cyclometalated ligand to form a new metalacycle: + H-C*~Z ⇄ + H-C~Y. Originally discovered for PdII complexes with Y/Z = N, P, S, the exchange appeared to be a mechanistically challenging, simple, and convenient routine for the synthesis of cyclopalladated complexes. Over four decades it was expanded to cyclometalated derivatives of platinum, ruthenium, manganese, rhodium, and iridium. The exchange, which is also questionably referred to as transcyclometalation, offers attractive synthetic possibilities and assists in disclosing key mechanistic pathways associated with the C–H bond activation by transition metal complexes and C–M bond cleavage. Both synthetic and mechanistic aspects of the exchange are reviewed and discussed.

scholarly journals Carbon-Hydrogen Bond Activation of Phenyldi(2- Thienyl)Phosphine at A Triruthenium Cluster Center

2012 ◽  
Vol 25 (1) ◽  
pp. 1-6 ◽  
Author(s):  
Shahed Rana ◽  
Shishir Ghosh ◽  
Shariff E Kabir
Keyword(s):  
Hydrogen Bond ◽  
Elemental Analysis ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Chemical Society ◽  
Cluster Center ◽  
Carbon Hydrogen Bond Activation

Ketyl-initiated reaction between Ru3(CO)12 and phenyldi(2-thienyl)phosphine (PhPTh2) furnished simple phosphine-substituted triruthenium clusters [Ru3(CO)10(PhPTh2)21 and [Ru3(CO)9(PhPTh2)3] 2. Heating 1 in boiling benzene afforded [Ru3(CO)8{?3- PhThP(C4H2S)}(PhPTh2)] 3 by carbon-hydrogen bond cleavage of a coordinated thienylphosphine ligand. All three new clusters have been characterized by elemental analysis, IR and NMR spectroscopic data.DOI: http://dx.doi.org/10.3329/jbcs.v25i1.11764 Journal of Bangladesh Chemical Society, Vol. 25(1), 1-6, 2012

scholarly journals DFT Study of Unstrained Ketone C-C Bond Activation via Rhodium(I)-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions

2019 ◽  
Author(s):  
Dengmengfei Xiao ◽  
Lili Zhao ◽  
Diego Andrada
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Chemical Reactivity ◽  
Cross Coupling ◽  
Underlying Mechanism ◽  
Reductive Elimination ◽  
Coupling Reactions ◽  
Co Catalysts ◽  
Cross Coupling Reactions ◽  
Strain Model

Unstrained cyclic ketones can participate in cooperative Suzuki-Miyaura cross-coupling type reaction using rhodium(I)-based catalyst via C-C bond activation. The regioselectivity indicates a trend where the most substituted side is activated and it is controlled by the beta-substituents. In this work, Density Functional Theory (DFT) calculations have been carried out to disclose the underlying mechanism in the reaction of a ketone series and arylboronate using ylidene as ancillary ligand and pyridine as co-catalysts. The computed energies suggest the reductive elimination step with the highest energy while the reductive elimination has the highest energy barrier. By the means of the Activation Strain Model (ASM) of chemical reactivity, it is found that the ketone strain energy released on the oxidative addition does not control the relativity of the OA reactivity, but indeed is the interaction energy between Rh(I) and C-C bond the ruling effect. The effect of the beta-substituents on regioselectivity has been additionally studied.

scholarly journals Steric C–N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2

2015 ◽  
Vol 51 (92) ◽  
pp. 16468-16471 ◽  
Author(s):  
Yan X. Shi ◽  
Rong Z. Liang ◽  
Katherine A. Martin ◽  
Daniel G. Star ◽  
Jesús Díaz ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Elemental Selenium ◽  
Cleavage Reaction ◽  
Ring Strain

The dimeric macrocyclophosphazane [{P(μ-NtBu)}2(μ-NtBu)]2 ( 1) was reacted with elemental selenium. An unexpected C–N cleavage reaction occurred producing P4(μ-NtBu)3(μ-NH)3Se4 ( 2). The C–N bond cleavage is driven by the high steric ring strain present within the ring.

Metal/Ligand Proton Tautomerism Facilitates Dinuclear H2 Reductive Elimination

2020 ◽  
Vol 142 (51) ◽  
pp. 21439-21449
Author(s):  
Jonathan L. Kuo ◽  
Karen I. Goldberg
Keyword(s):  
Reductive Elimination ◽  
Metal Ligand

Computational studies on Ni-catalyzed amide C–N bond activation

2019 ◽  
Vol 55 (76) ◽  
pp. 11330-11341 ◽  
Author(s):  
Hongliang Wang ◽  
Shuo-Qing Zhang ◽  
Xin Hong
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Mechanistic Models ◽  
Computational Studies

This review summarizes the mechanistic models of Ni-catalyzed amide C–N bond cleavage and discusses their applications in related transformations.

Co(i) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal–ligand cooperation platform

2020 ◽  
Vol 49 (41) ◽  
pp. 14592-14597
Author(s):  
Nai-Yuan Jheng ◽  
Yusuke Ishizaka ◽  
Yuki Naganawa ◽  
Akira Sekiguchi ◽  
Yumiko Nakajima
Keyword(s):  
Bond Cleavage ◽  
Metal Ligand

A cobalt(i) alkyl complex bearing a tetradentate phenanthroline-based PNNP ligand undergoes dearomatization of the ligand backbone skeleton upon heating and furthermore achieves H–H bond cleavage.

On the role of the surface oxygen species during A–H (A = C, N, O) bond activation: a density functional theory study

2015 ◽  
Vol 51 (13) ◽  
pp. 2621-2624 ◽  
Author(s):  
Jong Suk Yoo ◽  
Tuhin S. Khan ◽  
Frank Abild-Pedersen ◽  
Jens K. Nørskov ◽  
Felix Studt
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Oxygen Species ◽  
Final States ◽  
Surface Oxygen ◽  
Density Functional Theory Study ◽  
Reaction Energy ◽  
Functional Theory

During A–H (A = C, N, O) bond cleavage on O* or OH* pre-covered (111) surfaces, the oxygen species play the role of modifying the reaction energy by changing the species involved in the initial and final states of the reaction.

A coordinatively unsaturated iridium complex with an unsymmetrical redox-active ligand: (spectro)electrochemical and reactivity studies

2019 ◽  
Vol 48 (37) ◽  
pp. 13931-13942 ◽  
Author(s):  
Sebastian Sobottka ◽  
Margarethe Behr van der Meer ◽  
Estelle Glais ◽  
Uta Albold ◽  
Simon Suhr ◽  
...  
Keyword(s):  
Bond Activation ◽  
Iridium Complex ◽  
Iridium Complexes ◽  
Redox Active Ligand ◽  
Active Ligand ◽  
Redox Active ◽  
Metal Ligand

Metal–ligand cooperativity can be used in iridium complexes with an unsymmetrically substituted redox-active diamidobenzene ligand for bond activation reactions.

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