scholarly journals Synthesis of a copper-supported triplet nitrene complex pertinent to copper-catalyzed amination

Science ◽  
2019 ◽  
Vol 365 (6458) ◽  
pp. 1138-1143 ◽  
Author(s):  
Kurtis M. Carsch ◽  
Ida M. DiMucci ◽  
Diana A. Iovan ◽  
Alex Li ◽  
Shao-Liang Zheng ◽  
...  
Keyword(s):  
Multiple Bond ◽  
Transfer Reactions ◽  
Aryl Azides ◽  
Nitrene Transfer ◽  
Quantum Chemistry Calculations ◽  
Triplet Nitrene ◽  
X Ray Absorption ◽  
Dinitrogen Complex ◽  
Transfer Mechanisms ◽  
Bond Character

Terminal copper-nitrenoid complexes have inspired interest in their fundamental bonding structures as well as their putative intermediacy in catalytic nitrene-transfer reactions. Here, we report that aryl azides react with a copper(I) dinitrogen complex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrene complexes with near-linear, short copper–nitrenoid bonds [1.745(2) to 1.759(2) angstroms]. X-ray absorption spectroscopy and quantum chemistry calculations reveal a predominantly triplet nitrene adduct bound to copper(I), as opposed to copper(II) or copper(III) assignments, indicating the absence of a copper−nitrogen multiple-bond character. Employing electron-deficient aryl azides renders the copper nitrene species competent for alkane amination and alkene aziridination, lending further credence to the intermediacy of this species in proposed nitrene-transfer mechanisms.

scholarly journals A combined experimental and theoretical study on the reactivity of nitrenes and nitrene radical anions

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Yujing Guo ◽  
Chao Pei ◽  
Rene M. Koenigs
Keyword(s):  
Radical Anion ◽  
Room Temperature ◽  
Theoretical Study ◽  
Transition Metal Catalysts ◽  
Transfer Reactions ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Nitrene Transfer ◽  
Triplet Nitrene ◽  
Nitrogen Bonds

AbstractNitrene transfer reactions represent one of the key reactions to rapidly construct new carbon-nitrogen bonds and typically require transition metal catalysts to control the reactivity of the pivotal nitrene intermediate. Herein, we report on the application of iminoiodinanes in amination reactions under visible light photochemical conditions. While a triplet nitrene can be accessed under catalyst-free conditions, the use of a suitable photosensitizer allows the access of a nitrene radical anion. Computational and mechanistic studies rationalize the access and reactivity of triplet nitrene and nitrene radical anion and allow the direct comparison of both amination reagents. We conclude with applications of both reagents in organic synthesis and showcase their reactivity in the reaction with olefins, which underline their markedly distinct reactivity. Both reagents can be accessed under mild reaction conditions at room temperature without the necessity to exclude moisture or air, which renders these metal-free, photochemical amination reactions highly practical.

Collision-Induced Dissociations of Negative-Ions Formed by Reaction of HO- With Alkyl and Aryl Silanes. The Formation of Multiple Bonds to Silicon

1988 ◽  
Vol 41 (1) ◽  
pp. 57 ◽  
Author(s):  
RA Ohair ◽  
JH Bowie ◽  
GJ Currie
Keyword(s):  
Proton Transfer ◽  
Ab Initio Calculations ◽  
Collisional Activation ◽  
Multiple Bond ◽  
Negative Ions ◽  
Transfer Reactions ◽  
Multiple Bonds ◽  
Common Features ◽  
Proton Transfer Reactions ◽  
Bond Character

Collisional activation of alkyl and aryl siloxide ions produces a variety of ions and neutrals containing double bonds to silicon. Sila enolate ions and sila acyl ions RSi =O are common features of the spectra of alkylsiloxide ions; ab initio calculations suggest these ions to have considerable multiple bond character. It is proposed that most reactions proceed through ion complex intermediates. Specific proton transfer reactions often occur for ions Me3SiCHR (R = C3H5, C3H3 or Ph), i.e. Me3SiCHR → -CH2(Me)2SiCH2R. In the particular case of the formation of PhCH2- from Me3SiCHPh, i.e. Me3SiCHPh → -CH2(Me)2SiCH2Ph → PhCH2- +Me2Si=CH2, the proton transfer competes with scrambling of all hydrogens in the decomposing ion.

scholarly journals Synthesis and catalytic activity of μ-oxo ruthenium(IV) porphyrin species to promote amination reactions

2016 ◽  
Vol 20 (08n11) ◽  
pp. 1156-1165 ◽  
Author(s):  
Paolo Zardi ◽  
Daniela Intrieri ◽  
Daniela Maria Carminati ◽  
Francesco Ferretti ◽  
Piero Macchi ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Catalytic Activity ◽  
Single Crystal ◽  
General Formula ◽  
Catalytic Efficiency ◽  
Transfer Reactions ◽  
Aryl Azides ◽  
X Ray ◽  
Nitrene Transfer ◽  
Catalytically Active

This work describes the synthesis of ruthenium(IV) [Formula: see text]-oxo porphyrin complexes of general formula [RuIV(TPP)(X)]2O which have been applied as catalysts in nitrene transfer reactions using aryl azides (ArN[Formula: see text] as nitrene sources. Collected data indicated that the catalytic efficiency of [RuIV(TPP)(OCH[Formula: see text]]2O was comparable to that of RuII(TPP)CO because of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species RuVI(TPP)(ArN)2. The reaction of [RuIV(TPP)(OCH[Formula: see text]]2O with Ph3CN3 or (CH[Formula: see text]SiN3 afforded [RuIV(TPP)(N[Formula: see text]]2O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

Iron-Catalyzed Nitrene Transfer Reaction of 4-Hydroxystilbenes with Aryl Azides: Synthesis of Imines via C═C Bond Cleavage

2019 ◽  
Vol 21 (20) ◽  
pp. 8389-8394 ◽  
Author(s):  
Yi Peng ◽  
Yan-Hui Fan ◽  
Si-Yuan Li ◽  
Bin Li ◽  
Jing Xue ◽  
...  
Keyword(s):  
Transfer Reaction ◽  
Bond Cleavage ◽  
Aryl Azides ◽  
Nitrene Transfer

Multiple-bond character in Cp3U:CHPMe3: first low-temperature neutron diffraction analysis of a uranium organometallic complex

1990 ◽  
Vol 9 (3) ◽  
pp. 694-697 ◽  
Author(s):  
Raymond C. Stevens ◽  
Robert Bau ◽  
Roger E. Cramer ◽  
Dawood Afzal ◽  
John W. Gilje ◽  
...  
Keyword(s):  
Low Temperature ◽  
Neutron Diffraction ◽  
Diffraction Analysis ◽  
Multiple Bond ◽  
Organometallic Complex ◽  
Neutron Diffraction Analysis ◽  
Bond Character
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