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.

scholarly journals Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)3

2015 ◽  
Vol 6 (7) ◽  
pp. 4255-4260 ◽  
Author(s):  
A. L. Raza ◽  
T. Braun
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction ◽  
Consecutive Reactions ◽  
Silyl Complex

C–F activation reactions for a silyl complex gave fluorosilane and Rh pyridyl complexes. In consecutive reactions, the fluorosilane can act as a fluoride source and a regeneration of the C–F bond occurs by Si–F bond cleavage. This sets back the C–F bond cleavage reaction with consequences for the overall chemoselectivity of the activation reactions.

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 Efficient Synthesis of Carbovir and Its Congenerviaπ-Allylpalladium Complex Fomation by Ring Strain-Assisted C−N Bond Cleavage

1998 ◽  
Vol 63 (6) ◽  
pp. 2052-2052
Author(s):  
Nobuya Katagiri ◽  
Masahiro Takebayashi ◽  
Chikara Kaneko ◽  
Kouichi Kanehira ◽  
Masahiro Torihara
Keyword(s):  
Bond Cleavage ◽  
Efficient Synthesis ◽  
Ring Strain

Nitro–Nitrite Isomerization and Transition State Switching in the Dissociation of Ionized Nitromethane: A Threshold Photoelectron–Photoion Coincidence Spectroscopy Study

2009 ◽  
Vol 15 (2) ◽  
pp. 157-166 ◽  
Author(s):  
Brandon Ferrier ◽  
Anne-Marie Boulanger ◽  
David M.P. Holland ◽  
David A. Shaw ◽  
Paul M. Mayer
Keyword(s):  
Transition State ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Nitrite Ion ◽  
Methyl Nitrite ◽  
Bond Cleavage Reaction ◽  
Entropy Of Activation ◽  
Lower Entropy

Threshold photoelectron–photoion coincidence (TPEPICO) spectroscopy has been employed to investigate the competition between bond cleavage and rearrangement reactions in the dissociation of ionized nitromethane, 1. Modeling TPEPICO breakdown diagrams with a combination of RRKM theory and ab initio calculations at the G3 level of theory allowed the derivation of the activation energy for the isomerisation of 1 to ionized methyl nitrite, 2, 82 kJ mol−1. In addition, evidence was found for a transition state switch in the bond cleavage reaction in 1 leading to CH3• + NO2+. As internal energy increases, the effective transition state for this reaction becomes tighter (i.e. is characterized by a lower entropy of activation, Δ‡S). Fitted thresholds for NO+ and CH2OHO+ ions, originating from the isomeric methyl nitrite ion, are consistent with G3 level ab initio calculations.

Biosynthesis of C11 and C16 homoterpenes in higher plants; stereochemistry of the CC-bond cleavage reaction

Tetrahedron ◽  
1998 ◽  
Vol 54 (49) ◽  
pp. 14725-14736 ◽  
Author(s):  
Wilhelm Boland ◽  
Andreas Gäbler ◽  
Matthias Gilbert ◽  
Zhuofu Feng
Keyword(s):  
Higher Plants ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction

A novel CC bond cleavage reaction of 2, 2′-pyridil in solution

2010 ◽  
Vol 19 (11) ◽  
pp. 1116-1118
Author(s):  
Rui Ren ◽  
Pin Yang ◽  
Xiang-Lin Jin
Keyword(s):  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction

scholarly journals Theoretical Study of the Ti–Cl Bond Cleavage Reaction in TiCl4

2017 ◽  
Vol 231 (9) ◽  
Author(s):  
Daniel Nurkowski ◽  
Ahren W. Jasper ◽  
Jethro Akroyd ◽  
Markus Kraft
Keyword(s):  
Theoretical Study ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction ◽  
Kinetics Of

AbstractIn this work the kinetics of the TiCl

ChemInform Abstract: Zinc-Acetic Acid Promoted Reductive Carbon-Nitrogen Bond Cleavage Reaction of α-Aminoketones.

ChemInform ◽  
2014 ◽  
Vol 45 (24) ◽  
pp. no-no
Author(s):  
Hideaki Fujii ◽  
Kyoko Ishikawa ◽  
Miyuki Tomatsu ◽  
Hiroshi Nagase
Keyword(s):  
Acetic Acid ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction ◽  
Nitrogen Bond

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

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