Reactivity of [Os3(μ-H)2(CO)10] with N-Heterocyclic Carbenes: A Combined Experimental and DFT Computational Study§

2010 ◽  
Vol 29 (17) ◽  
pp. 3828-3836 ◽  
Author(s):  
Javier A. Cabeza ◽  
Ignacio del Río ◽  
José M. Fernández-Colinas ◽  
Enrique Pérez-Carreño ◽  
M. Gabriela Sánchez-Vega ◽  
...  
Keyword(s):  
Computational Study ◽  
Heterocyclic Carbenes

Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

2015 ◽  
Vol 44 (46) ◽  
pp. 20021-20026 ◽  
Author(s):  
A. Pazio ◽  
K. Woźniak ◽  
K. Grela ◽  
B. Trzaskowski
Keyword(s):  
Olefin Metathesis ◽  
Computational Study ◽  
Heterocyclic Carbenes ◽  
Mechanistic Study ◽  
Nitrenium Ions ◽  
Nitrenium Ion ◽  
Metathesis Catalysts

A DFT mechanistic study reveals that nitrenium ion-modified Hoveyda-like complexes are good candidates for latent metathesis catalysts, while boron-modified systems are candidates for very fast metathesis catalysts.

Theoretical Investigation of Main-Group Element Hydride Insertion into Phosphorus-Heterocyclic Carbenes (PHCs)

2020 ◽  
Vol 73 (8) ◽  
pp. 787
Author(s):  
Khalidah H. M. Al Furaiji ◽  
Andrew Molino ◽  
Jason L. Dutton ◽  
David J. D. Wilson
Keyword(s):  
Computational Study ◽  
Ring Expansion ◽  
Heterocyclic Ring ◽  
Main Group ◽  
Heterocyclic Carbenes ◽  
Group Element ◽  
Steric Effects ◽  
Main Group Element ◽  
Theoretical Investigations ◽  
Electronic And Steric Effects

Initial reports of ring expansion reactions (RER) of N-heterocyclic carbenes (NHCs) with main-group element hydrides have led to several synthetic and theoretical investigations, which include reports of insertion by Be, B, Al, Si, and Zn hydrides. The RERs generally lead to insertion of the heteroatom into the endocyclic C–N bond with formation of an expanded heterocyclic ring. Following the recent isolation of a P-heterocyclic carbene (PHC), here we report results from a computational study (RI-SCS-MP2/def2-TZVP//M06–2X/def2-TZVP) of RERs with a series of PHCs for the ring-insertion of silicon (SiH4, SiH2Ph2) and boron (BH3, BH2NMe2) hydrides. In order to explore the roles of both electronic and steric effects on PHCs and their reactivity, a series of P-substituent PHCR (R=H, Me, Ph, and bulky Ar groups) were investigated. Bulky R groups serve to maximise ring planarity and the σ-donating capability of the PHC. For RER, the PHC analogues exhibit facile initial hydride transfer from the main-group hydrides to the carbene carbon, with barriers that are substantially lower than with NHCs. However, the full ring insertion mechanisms for PHCs are, in general, kinetically unfavourable due to a large barrier associated with the ring-expansion step. While bulky P-substituents maximise heterocycle planarity towards that of NHCs, the RER reactivity with bulky PHCs does not reflect that of an NHC.

scholarly journals On the Bonding Situation in Stannocene and Plumbocene N-Heterocyclic Carbene Complexes

2019 ◽  
Author(s):  
Diego Andrada ◽  
Sergi Danés ◽  
Lisa Wirtz ◽  
Carsten Mueller ◽  
Volker Huch ◽  
...  
Keyword(s):  
Computational Study ◽  
Decomposition Analysis ◽  
Heterocyclic Carbenes ◽  
Lewis Base ◽  
Energy Decomposition Analysis ◽  
Dispersion Interactions ◽  
X Ray Diffraction ◽  
Group 14 ◽  
Carbene Complexes ◽  
Covalent Interactions

A detailed experimental and computational study of a series of stannocene and plumbocene N-heterocyclic carbene complexes is presented. This unique class of group 14 Lewis acid base adducts was obtained from reactions of the corresponding metallocenes and N-heterocyclic carbenes (NHC), and were structurally characterized by single crystal X-ray diffraction. The obtained structures show a perpendicular pose of the NHC with respect to the metallocene, hence precluding the maximal interaction between the moieties. The nature of the Sn-CNHC and Pb-CNHC bonds have been investigated by applying Energy Decomposition Analysis (EDA-NOCV). For the sake of comparison, known stannocene and plumbocene Lewis base complexes have been included in the series. The attractive chemical bonding interactions are around 50% electrostatic, 30% covalent and 20% dispersion. Indeed, dispersion interactions play a determining role the bigger the substituents become. The covalent interactions derive from the donation of the carbene ligand into the empty p orbital of the metallocene.

A comparative computational study of N-heterocyclic olefin and N-heterocyclic carbene mediated carboxylative cyclization of propargyl alcohols with CO2

2016 ◽  
Vol 14 (46) ◽  
pp. 10875-10885 ◽  
Author(s):  
Weiyi Li ◽  
Dongfeng Huang ◽  
Yajing Lyu
Keyword(s):  
Catalytic Effect ◽  
Computational Study ◽  
Side Reaction ◽  
Heterocyclic Carbenes ◽  
Propargyl Alcohols

N-heterocyclic olefins are more efficient than N-heterocyclic carbenes for the carboxylative cyclization of propargyl alcohols with CO2. They also have less of a catalytic effect on the side reaction.

Diboryne Nanostructures Stabilized by Multitopic N-Heterocyclic Carbenes: A Computational Study

2018 ◽  
Vol 57 (7) ◽  
pp. 3931-3940 ◽  
Author(s):  
Felipe Fantuzzi ◽  
Caroline B. Coutinho ◽  
Ricardo R. Oliveira ◽  
Marco Antonio Chaer Nascimento
Keyword(s):  
Computational Study ◽  
Heterocyclic Carbenes

scholarly journals On the Bonding Situation in Stannocene and Plumbocene N-Heterocyclic Carbene Complexes

2019 ◽  
Author(s):  
Diego Andrada ◽  
Sergi Danés ◽  
Lisa Wirtz ◽  
Carsten Mueller ◽  
Volker Huch ◽  
...  
Keyword(s):  
Computational Study ◽  
Decomposition Analysis ◽  
Heterocyclic Carbenes ◽  
Lewis Base ◽  
Energy Decomposition Analysis ◽  
Dispersion Interactions ◽  
X Ray Diffraction ◽  
Group 14 ◽  
Carbene Complexes ◽  
Covalent Interactions

A detailed experimental and computational study of a series of stannocene and plumbocene N-heterocyclic carbene complexes is presented. This unique class of group 14 Lewis acid base adducts was obtained from reactions of the corresponding metallocenes and N-heterocyclic carbenes (NHC), and were structurally characterized by single crystal X-ray diffraction. The obtained structures show a perpendicular pose of the NHC with respect to the metallocene, hence precluding the maximal interaction between the moieties. The nature of the Sn-CNHC and Pb-CNHC bonds have been investigated by applying Energy Decomposition Analysis (EDA-NOCV). For the sake of comparison, known stannocene and plumbocene Lewis base complexes have been included in the series. The attractive chemical bonding interactions are around 50% electrostatic, 30% covalent and 20% dispersion. Indeed, dispersion interactions play a determining role the bigger the substituents become. The covalent interactions derive from the donation of the carbene ligand into the empty p orbital of the metallocene.

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