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

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.

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Oxidative C–S bond cleavage reaction of DMSO for C–N and C–C bond formation: new Mannich-type reaction for β-amino ketones

RSC Advances ◽

10.1039/c4ra14249g ◽

2015 ◽

Vol 5 (4) ◽

pp. 3094-3097 ◽

Cited By ~ 19

Author(s):

Kai Sun ◽

Yunhe Lv ◽

Zhonghong Zhu ◽

Liping Zhang ◽

Hankui Wu ◽

...

Keyword(s):

Bond Cleavage ◽

Bond Formation ◽

Cleavage Reaction ◽

Type Reaction ◽

Bond Cleavage Reaction

A novel oxidative C–S bond cleavage reaction of DMSO for N-methylation and subsequent C–C bond formation is described.

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ChemInform Abstract: Oxidative C-S Bond Cleavage Reaction of DMSO for C-N and C-C Bond Formation: New Mannich-Type Reaction for β-Amino Ketones.

ChemInform ◽

10.1002/chin.201523042 ◽

2015 ◽

Vol 46 (23) ◽

pp. no-no

Author(s):

Kai Sun ◽

Yunhe Lv ◽

Zhonghong Zhu ◽

Liping Zhang ◽

Hankui Wu ◽

...

Keyword(s):

Bond Cleavage ◽

Bond Formation ◽

Cleavage Reaction ◽

Type Reaction ◽

Bond Cleavage Reaction

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Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

10.26434/chemrxiv.11742687 ◽

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.

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

European Journal of Mass Spectrometry ◽

10.1255/ejms.943 ◽

2009 ◽

Vol 15 (2) ◽

pp. 157-166 ◽

Cited By ~ 6

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.

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