NDLI: Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study

Please wait, while we are loading the content...

Hydrogen photogeneration from water on the biomimetic hybrid artificial photocatalytic systems of semiconductors and earth-abundant metal complexes: progress and challenges

Rational design of carbon support to prepare ultrafine iron oxide catalysts for air oxidation of alcohols

Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al₂O₃ catalyst

SnO₂-isolated Pt₃Sn alloy on reduced graphene oxide: an efficient catalyst for selective hydrogenation of CO in unsaturated aldehydes

Palladium N-heterocyclic carbene catalyzed regioselective C–H halogenation of 1-aryl-3-methyl-1H-pyrazol-5(4H)-ones using N-halosuccinimides (NXS)

Attrition-resistant Ni–Mg/Al₂O₃ catalyst for fluidized bed syngas methanation

Sporopollenin as an efficient green support for covalent immobilization of a lipase ( Catalysis Science & Technology Vol - 5 Issue - 6 )

Improving mass-transfer in controlled pore glasses as supports for the platinum-catalyzed aromatics hydrogenation

Comparison of catalytic properties of supported metal oxides for benzene oxidation using ozone

A facile strategy for enhancing FeCu bimetallic promotion for catalytic phenol oxidation

Low-temperature CO oxidation on CuO/CeO₂ catalysts: the significant effect of copper precursor and calcination temperature

Cubic Pm3n mesoporous aluminosilicates assembled from zeolite seeds as strong acidic catalysts

A novel magnetic palladium catalyst for the mild aerobic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid in water

Catalytic reduction of NO by CO on Rh₄⁺ clusters: a density functional theory study

Flower-like Au/Ni–Al hydrotalcite with hierarchical pore structure as a multifunctional catalyst for catalytic oxidation of alcohol

Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu–Mo/TiO₂

Synthesis and characterization of Pd(ii) dispersed over diamine functionalized graphene oxide and its scope as a catalyst for selective oxidation

Lignin depolymerization over Ni/C catalyst in methanol, a continuation: effect of substrate and catalyst loading

CO tolerance of a Pt₃Sn(111) catalyst in ethanol decomposition

Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study

Synthesis of tungsten carbide nanoparticles in biochar matrix as a catalyst for dry reforming of methane to syngas

Significant effect of base on the improvement of selectivity in the hydrogenation of benzoic acid over NiZrB amorphous alloy supported on γ-Al₂O₃

Synthesis of novel MgAl layered double oxide grafted TiO₂ cuboids and their photocatalytic activity on CO₂ reduction with water vapor

Solid-phase synthesis of recyclable diphosphine ligands

Synthesis and characterization of rare-earth metal complexes supported by a new pentadentate Schiff base and their application in heteroselective polymerization of rac-lactide

Selective hydrogenation of cinnamaldehyde on nickel nanoparticles supported on titania: role of catalyst preparation methods

Reexamination of formic acid decomposition on the Pt(111) surface both in the absence and in the presence of water, from periodic DFT calculations

(Pd–CuCl₂)/γ-Al₂O₃: a high-performance catalyst for carbonylation of methyl nitrite to dimethyl carbonate

Optimization of the catalytic hydrogenation of terebinth by a Ni-based catalyst

Mechanism of N-heterocylic carbene-catalyzed annulation of allenals with chalcones to 3-pyrancarbaldehydes or cyclopentene

Synthesis of fluorenones by using Pd(ii)/Mg–La mixed oxide catalyst

CdS-decorated triptycene-based polymer: durable photocatalysts for hydrogen production under visible-light irradiation

Ternary mesoporous WO₃/Mn₃O₄/N-doped graphene nanocomposite for enhanced photocatalysis under visible light irradiation

Study on the one-pot oxidative esterification of glycerol with MOF supported polyoxometalates as catalyst

Cyclohexane oxidation over AFI molecular sieves: effects of Cr, Co incorporation and crystal size

Nickel and cobalt phosphides as effective catalysts for oxygen removal of dibenzofuran: role of contact time, hydrogen pressure and hydrogen/feed molar ratio

Facile structure design based on C₃N₄ for mediator-free Z-scheme water splitting under visible light

Correction: Simple hydrothermal synthesis of mesoporous spinel NiCo₂O₄ nanoparticles and their catalytic behavior in CH₃OH electro-oxidation and H₂O₂ electro-reduction

Sporopollenin as an efficient green support for covalent immobilization of a lipase ( Catalysis Science & Technology Vol - 5 Issue - 6 )

Back cover

Catalysis Science & Technology Vol - 5 Issue - 5

Catalysis Science & Technology Vol - 5 Issue - 4

Catalysis Science & Technology Vol - 5 Issue - 3

Catalysis Science & Technology Vol - 5 Issue - 2

Catalysis Science & Technology Vol -4

Catalysis Science & Technology Vol -3

Catalysis Science & Technology Vol -2

Catalysis Science & Technology Vol -1

Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study

Content Provider	Royal Society of Chemistry (RSC)
Author	Wei, Haiyan Huang, Liangfang Wei, Xiaoqin Wang, Jiandi
Copyright Year	2015
Abstract	The reduction of organic substrates using high-valent oxo-transition metal complexes represents a new catalytic activity. In this study, we theoretically investigated the mechanism of catalytic reduction of amides, amines, nitriles and sulfoxides with boranes by the high-valent di-oxo-molybdenum(VI) complex MoO2Cl2. Our computational results reveal that reduction of sulfoxides with boranes catalyzed by MoO2Cl2 proceeds via a [2 + 2] addition pathway involving the B–H bond of borane adding across the MoO bond to form a metal hydride intermediate, followed by the elimination of the new species HOBcat, accompanied by the loss of the sulfide. The activation free energy of the turnover-limiting step is calculated to be 24.0 kcal mol−1. By contrast, borane additions to either amide, amine or nitrile proceed through an ionic outer-sphere mechanism, in which the substrates attack the boron center to prompt the heterolytic cleavage of the B–H bond, generating an anionic molybdenum(VI) hydride paired with a borylated amide/amine/nitrile cation. Then, the activated organic substrates abstract a hydride from the molybdenum(VI) center to complete the catalytic cycle. The activation free energies of the turnover-limiting step along the ionic outer-sphere pathway are calculated to be ~22.7, 19.7 and 30.6 kcal mol−1 for benzamide, N-(diphenylmethylene)benzenamine, and benzonitrile, respectively. These values are energetically more favorable (~3–8.0 kcal mol−1) than those via the [2 + 2] addition pathway. Along the ionic outer-sphere pathway, the multiply bonded oxo ligand does not participate in the activation of the B–H bond. The ionic outer-sphere mechanism suggests that the high-valent di-oxo-molybdenum(VI) complex MoO2Cl2 acts as a Lewis acid in catalyzing the reduction reaction and activation of B–H bonds.
Starting Page	3259
Ending Page	3269
Page Count	11
File Format	HTM / HTML PDF
ISSN	20444753
Volume Number	5
Issue Number	6
Journal	Catalysis Science & Technology
DOI	10.1039/c5cy00177c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Sulfide Gibbs free energy Nitrile Ligand Ion Molybdenum Benzamide Benzonitrile Boron Carboxylic acid Covalent bond Amide Hydride Catalytic cycle
Content Type	Text
Resource Type	Article
Subject	Catalysis

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Mechanistic insights into hydrogen generation for catalytic hydrolysis and alcoholysis of silanes with high-valent oxorhenium(v) complexes

Expanding the role of oxo-molybdenum(vi) catalysts: a DFT interpretation of X–H activation leading to reduction or oxidation

CH Bond Activation during and after the Reactions of a Metallacyclic Amide with Silanes: Formation of a μ-Alkylidene Hydride Complex, Its H–D Exchange, and β-H Abstraction by a Hydride Ligand

Boron(8) substituted nitrilium and ammonium derivatives, versatile cobalt bis(1,2-dicarbollide) building blocks for synthetic purposes

1,2-Bis(2-oxo-azepane-1-carboxylic acid-p-phenyl-amide)ethane and 1-(2-Oxo-azepane-1-carboxylic Acid-o-phenyl-amide)-2-(2-oxo-azepane-1-carboxylic acid-p-phenyl-amide)ethane

Dioxidomolybdenum(VI) complex featuring a 2,4-di-fluoro-substituted amine bis-(phenolate) ligand.

Rhodium(iii)-catalyzed intramolecular annulations involving amide-directed C–H activations: synthetic scope and mechanistic studies

Binary reducing agents containing dichloroindium hydride for the selective, partial, or tandem reductions of bifunctional compounds consisting of halo-nitriles, halo-esters and halo-carboxylic acids

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds

Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study

Similar Documents

Mechanistic insights into hydrogen generation for catalytic hydrolysis and alcoholysis of silanes with high-valent oxorhenium(v) complexes

Expanding the role of oxo-molybdenum(vi) catalysts: a DFT interpretation of X–H activation leading to reduction or oxidation

CH Bond Activation during and after the Reactions of a Metallacyclic Amide with Silanes: Formation of a μ-Alkylidene Hydride Complex, Its H–D Exchange, and β-H Abstraction by a Hydride Ligand

Boron(8) substituted nitrilium and ammonium derivatives, versatile cobalt bis(1,2-dicarbollide) building blocks for synthetic purposes

1,2-Bis(2-oxo-azepane-1-carboxylic acid-p-phenyl-amide)ethane and 1-(2-Oxo-azepane-1-carboxylic Acid-o-phenyl-amide)-2-(2-oxo-azepane-1-carboxylic acid-p-phenyl-amide)ethane

Dioxidomolybdenum(VI) complex featuring a 2,4-di-fluoro-substituted amine bis-(phenolate) ligand.

Rhodium(iii)-catalyzed intramolecular annulations involving amide-directed C–H activations: synthetic scope and mechanistic studies

Binary reducing agents containing dichloroindium hydride for the selective, partial, or tandem reductions of bifunctional compounds consisting of halo-nitriles, halo-esters and halo-carboxylic acids

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds

Does a multiply bonded oxo ligand directly participate in B–H bond activation by a high-valent di-oxo-molybdenum(vi) complex? A density functional theory study