Understanding the insertion reactions of CO2, aldehyde and alkene into Cu–X (X = B, C, O) bonds

2021 ◽  
Author(s):  
Xueying Guo ◽  
Zhenyang Lin
Keyword(s):  
Dft Calculations ◽  
Organic Molecules ◽  
Insertion Reactions ◽  
Relative Preference

The relative preference of different unsaturated organic molecules (CO2, PhCHO and styrene) for insertion into different Cu–X (X = B, C, O) bonds has been systematically examined with the aid of DFT calculations.

The chemistry of stabilized clusters

1982 ◽  
Vol 308 (1501) ◽  
pp. 27-34 ◽  
Keyword(s):  
Electron Donor ◽  
Organic Molecules ◽  
Metal Cluster ◽  
Organic Substrates ◽  
Insertion Reactions ◽  
Donor Ligand ◽  
Small Organic Molecules ◽  
Wide Range ◽  
Metal Metal ◽  
High Yields

Studies of the chemistry of metal cluster complexes and, in particular, their reactions with small organic molecules, have been confined to relatively few systems. Among the reasons for this are: (i) not many clusters are easily synthesized in high yields; (ii) their reactions often give a multitude of products that are difficult to separate and characterize; (iii) the conditions required to bring about reactions often lead to fragmentation of the cluster into lower nuclearity (often mononuclear) species. One cluster whose chemistry has been extensively studied is [Os 3 H 2 (CO) 10 ]. This can be synthesized in high yields from [Os 3 (CO) 12 ] + H 2 (Knox et al. 1975) and reacts readily under mild conditions with a wide range of electron-donor molecules by virtue of its coordinative unsaturation (Shapley et al. 1975; Deeming & Hasso 1976; Adams & Golembeski 1979). Formally, one may consider that a metal—metal double bond is present, which is reduced to a single bond on coordination of an additional two-electron donor ligand such as an organophosphine. The presence of metal—hydrogen bonds in this cluster and the cluster’s ability to coordinate organic substrates enable it to undergo a wide variety of insertion reactions, leading to products that may be regarded as intermediates in the reduction of organic molecules by clusters (Deeming & Hasso 1975; Keister & Shapley 1975).

Competition between coordination bonds and hydrogen bonding interactions in solvatomorphs of copper(II), cadmium(II) and cobalt(II) complexes with 2,2′-bipyridyl and acetate

2019 ◽  
Vol 234 (2) ◽  
pp. 119-128 ◽  
Author(s):  
José Antônio do Nascimento Neto ◽  
Cameron Capeletti da Silva ◽  
Leandro Ribeiro ◽  
Ana Karoline Silva Mendanha Valdo ◽  
Felipe Terra Martins
Keyword(s):  
Hydrogen Bonding ◽  
Dft Calculations ◽  
Organic Molecules ◽  
Energy Difference ◽  
Water Molecules ◽  
Coordination Numbers ◽  
Lattice Water ◽  
Hydrogen Bonding Interactions ◽  
Metal Organic ◽  
Coordination Bonds

Abstract The delicate balance among conformation, coordination bonds and hydrogen bonding has been probed in solvatomorphs of known metal-organic molecules synthesised from copper(II), cadmium(II) and cobalt(II) with acetate (OAc) and 2,2′-bipyridine (bipy). The Cu(OAc)2(bipy) complex, isolated as a pentahydrate, has the acetate ligands oriented to opposite sides of the coordination square plane. DFT calculations show the energy difference between this structure and a syn form amount to approximately 16 kJ/mol. The presence of lattice water enables the formation of O–H···O hydrogen bonds with the acetate ligands. Different coordination numbers and energies are found as a function of the number of water molecules co-crystallising in the Cd(OAc)2(bipy)(OH2)·3H2O and [Co(OAc)(bipy)2](OAc)·3H2O complexes.

A DFT STUDY OF CO MIGRATORY INSERTION REACTIONS WITH A NEW TYPE OF GROUP 10 METAL-ALKYL AND METAL-ALKOXIDE BONDS

2012 ◽  
Vol 11 (01) ◽  
pp. 1-17 ◽  
Author(s):  
SIWEI BI ◽  
JUNFENG ZHAO ◽  
WEI FAN ◽  
PING LI
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Metal Alkoxide ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Step Process ◽  
Migratory Insertion ◽  
One Step ◽  
New Type

The CO migratory insertion into M–O and M–C bonds of the new model (PMe3)2M(η2 – CH2CH2O) ( M = Ni , Pd and Pt ) (model (d)) proposed in this work has been studied with the aid of density functional theory (DFT) calculations. It is found (1) when M = Ni , CO migratory insertion into Ni–C is thermodynamically and kinetically favored, and (2) when M = Pd and Pt , the insertion into M–O bond via a one-step process is preferred. Further investigation on CO migratory insertion using Pt(PMe3)2(C7H10O) (R′-Pt) derived from the experimental compound Pt(PEt3)2(C7H10O) gives the same conclusions as model (d) with M = Pt . Results obtained from the reaction of model (d) ( M = Pt ) with CO are consistent with the experimental observation that CO prefers to insert into Pt–O bond of Pt(PEt3)2(C7H10O) .

A computational mechanistic study of substrate-controlled competitive O–H and C–H insertion reactions catalyzed by dirhodium(ii) carbenoids: insight into the origin of chemoselectivity

2018 ◽  
Vol 5 (15) ◽  
pp. 2353-2363 ◽  
Author(s):  
Li-Han Zhu ◽  
Hai-Yan Yuan ◽  
Wen-Liang Li ◽  
Jing-Ping Zhang
Keyword(s):  
Dft Calculations ◽  
Mechanistic Study ◽  
Insertion Reactions ◽  
Rhodium Carbenoid ◽  
Insight Into

DFT calculations disclosed the chemoselectivity of rhodium carbenoid and water co-catalyzed O–H and C–H insertion reactions with three 1,3-diketone substrates.

Halodiazoacetates as useful tools for selective halo-functionalization

2011 ◽  
Vol 83 (3) ◽  
pp. 565-575 ◽  
Author(s):  
Hanne Therese Bonge ◽  
Tore Hansen
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Diazo Compounds ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Kinetic Activity ◽  
Synthetic Utility ◽  
Insight Into ◽  
Halocarbonyl Compounds

The halodiazoacetates are a group of synthetically useful halogenated diazo compounds that can be used in Rh(II)-catalyzed carbenoid reactions. In the reactions between the halodiazoacetates and electron-rich, sterically unhindered alkenes, halocyclopropanes are formed in good to excellent yields. The halodiazoacetates also react well in C–H and Si–H insertion reactions, broadening the synthetic utility of these reactions. The products of the reactions are synthetically useful α-halocarbonyl compounds. Density functional theory (DFT) calculations have given insight into the mechanism of the cyclopropanation and C–H insertion reactions of the halodiazoacetates, and have also shown that the halodiazoacetates have a particularly high kinetic activity.

An INS study of entrapped organic cations within the micropores of zeolite RTH

2016 ◽  
Vol 18 (26) ◽  
pp. 17244-17252 ◽  
Author(s):  
Tetiana Lemishko ◽  
Jorge Simancas ◽  
Manuel Hernández-Rodríguez ◽  
Mónica Jiménez-Ruiz ◽  
German Sastre ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Organic Molecules ◽  
Organic Cations

INS experiments and DFT calculations allow identifying rotational constraints of organic molecules occluded in zeolite micropores.

scholarly journals Effect of an Al(III) Complex on the Regio- and Stereoisomeric Formation of Bicyclic Organic Carbonates

2020 ◽  
Author(s):  
Cristina Maquilón ◽  
Bart Limburg ◽  
Victor Laserna ◽  
Diego Garay-Ruiz ◽  
Joan González Fabra ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Dft Calculations ◽  
Organic Molecules ◽  
Solid Phase ◽  
Starting Material ◽  
X Ray ◽  
Epoxy Alcohol ◽  
Organic Carbonates ◽  
Presence And Absence

Valorization of carbon dioxide into organic molecules using catalytic approaches has witnessed an upsurge in recent years. Here, the influence of an Al(III) aminotriphenolate complex on the regio- and stereo-chemical features of the coupling between carbon dioxide and a cyclic epoxy alcohol has been studied. Three distinct bicyclic carbonate products were produced from a single starting material depending on the catalytic conditions. The proposed carbonate configurations were examined by solution and solid phase techniques including NMR spectroscopic and X-ray crystallographic analyses. Control experiments combined with DFT calculations provide a rationale for the distinct catalytic manifolds observed in the presence and absence of the Al(III) complex.

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