C-O Bond Activation by a Tantalum-Bonded Pincer Ligand - Ligand Modification Effects on the Selectivity of C-H Bond Cleavage Processes

2014 ◽  
Vol 2014 (36) ◽  
pp. 6196-6204 ◽  
Author(s):  
Rosa Fandos ◽  
Carolina Hernández ◽  
Antonio Otero ◽  
Ana Rodríguez ◽  
María José Ruiz
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Pincer Ligand ◽  
Ligand Modification

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 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.

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.

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.

Cooperative Bond Activation Reactions with Nickel and Palladium Carbene Complexes with a PCcarbeneS Pincer Ligand

2019 ◽  
Vol 38 (21) ◽  
pp. 4093-4104 ◽  
Author(s):  
Lennart T. Scharf ◽  
Alexander Kowsari ◽  
Thorsten Scherpf ◽  
Kai-Stephan Feichtner ◽  
Viktoria H. Gessner
Keyword(s):  
Bond Activation ◽  
Pincer Ligand ◽  
Carbene Complexes

scholarly journals Heterolytic bond activation at gold: evidence for gold(iii) H–B, H–Si complexes, H–H and H–C cleavage

2019 ◽  
Vol 10 (9) ◽  
pp. 2633-2642 ◽  
Author(s):  
Luca Rocchigiani ◽  
Peter H. M. Budzelaar ◽  
Manfred Bochmann
Keyword(s):  
Dft Calculations ◽  
Bond Activation ◽  
Bond Cleavage

Gold(iii) forms spectroscopically detectable H–B and H–Si σ-complexes; experiments and DFT calculations demonstrate heterolytic H–Si, H–H and H–C bond cleavage.

Palladium-catalyzed C(carbonyl)–C bond cleavage of amides: a facile access to phenylcarbamate derivatives with alcohols

2018 ◽  
Vol 54 (62) ◽  
pp. 8606-8609 ◽  
Author(s):  
Xufei Yan ◽  
Huihui Sun ◽  
Haifeng Xiang ◽  
Da-Gang Yu ◽  
Daibing Luo ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Palladium Catalyzed ◽  
Sulfur Containing

A sulfur-containing auxiliary enabled palladium-catalyzed C(carbonyl)–C bond activation of amides was reported to form phenylcarbamate derivatives with alcohols.

Carbonfluorine bond activation by iron(I). CF bond cleavage induced by addition of phosphines or thiols to a perfluorovinyldiiron complex

1997 ◽  
Vol 533 (1-2) ◽  
pp. 177-185 ◽  
Author(s):  
René Rumin ◽  
Karine Guennou ◽  
Roger Pichon ◽  
François Y. Pétillon ◽  
Kenneth W. Muir ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage
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