NDLI: Boron–boron <i>J</i> coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

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

Roles of carboxylate donors in O–O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) with a new carboxylate-containing dinucleating ligand

Exciton recombination dynamics in nanoring cycloparaphenylenes

Zinc-seamed pyrogallol[4]arene dimers as structural components in a two-dimensional MOF

Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H₂O₂ generation vs. O–O bond cleavage

Illuminating HIV gp120-ligand recognition through computationally-driven optimization of antibody-recruiting molecules

Construction of an orthogonal ZnSalen/Salophen library as a colour palette for one- and two-photon live cell imaging

Highly sensitive and selective detection of the pyrophosphate anion biomarker under physiological conditions

Pd(quinox)-catalyzed allylic relay Suzuki reactions of secondary homostyrenyl tosylates via alkene-assisted oxidative addition

Metal control of selectivity in acetate-assisted C–H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp²)–H bonds at Ir and Rh

A catalyst-controlled selective synthesis of pyridines and pyrroles

Non-directed allylic C–H acetoxylation in the presence of Lewis basic heterocycles

Formal hydrogenation of arynes with silyl C_β–H bonds as an active hydride source

Rapid, facile synthesis of conjugated polymer zwitterions in ionic liquids

Coordination-triggered NO release from a dinitrosyl iron complex leads to anti-inflammatory activity

Copper catalyzed direct alkenylation of simple alkanes with styrenes

Synthesis of diarylmethylamines via palladium-catalyzed regioselective arylation of 1,1,3-triaryl-2-azaallyl anions

Guest-dependent mechanical anisotropy in pillared-layered soft porous crystals – a nanoindentation study

Disubstituted sialic acid ligands targeting siglecs CD33 and CD22 associated with myeloid leukaemias and B cell lymphomas

5-(Methylthio)tetrazoles as versatile synthons in the stereoselective synthesis of polycyclic pyrazolines via photoinduced intramolecular nitrile imine–alkene 1,3-dipolar cycloaddition

Copper catalyzed Heck-like cyclizations of oxime esters

Selective radical amination of aldehydic C(sp²)–H bonds with fluoroaryl azides via Co(ii)-based metalloradical catalysis: synthesis of N-fluoroaryl amides from aldehydes under neutral and nonoxidative conditions

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Enantioselective direct α-alkylation of cyclic ketones by means of photo-organocatalysis

Addition of pnictogen atoms to chromium(ii): synthesis, structure and magnetic properties of a chromium(iv) phosphide and a chromium(iii) arsenide

Sequence-responsive unzipping DNA cubes with tunable cellular uptake profiles

Pattern-based sensing of aminoglycosides with fluorescent amphiphiles

Spin crossover iron(ii) complexes as PARACEST MRI thermometers

Phosphorus(v) tetraazaporphyrins: porphyrinoids showing an exceptionally strong CT band between the Soret and Q bands

Magnitude and consequences of OR ligand σ-donation on alkene metathesis activity in d⁰ silica supported (SiO)W(NAr)(CHtBu)(OR) catalysts

Phosphorescent nematic hydrogels and chromonic mesophases driven by intra- and intermolecular interactions of bridged dinuclear cyclometalated platinum(ii) complexes

The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium(iv) and uranium(iv) alkyls

Facile dissolution of selenium and tellurium in a thiol–amine solvent mixture under ambient conditions

X-ray fluorescence imaging reveals subcellular biometal disturbances in a childhood neurodegenerative disorder

Carbon–fluorine bond cleavage in fluoroarenes via a niobium(iii) imido complex: from stoichiometric to catalytic hydrodefluorination

Ambient condition oxidation in individual liposomes observed at the single molecule level

Detecting intracellular translocation of native proteins quantitatively at the single cell level

Conformational control of anticancer activity: the application of arene-linked dinuclear ruthenium(ii) organometallics

Multiple metal-bound oligomers from Ir-catalysed dehydropolymerisation of H₃B·NH₃ as probed by experiment and computation

Aqueous solubilization of hydrophobic supramolecular metal–organic nanocapsules

Stimuli-induced folding cascade of a linear oligomeric guest chain programmed through cucurbit[n]uril self-sorting (n = 6, 7, 8)

Mapping electrogenerated chemiluminescence reactivity in space: mechanistic insight into model systems used in immunoassays

Tuning the electronic environment of cations and anions using ionic liquid mixtures

En route towards panchromatic light harvesting: photophysical and electrochemical properties of Bodipy–porphyrazine conjugates

Back cover

Chemical Science Vol - 5 Issue - 5

Chemical Science Vol - 5 Issue - 4

Chemical Science Vol - 5 Issue - 3

Chemical Science Vol - 5 Issue - 2

Chemical Science Vol -4

Chemical Science Vol -3

Chemical Science Vol -2

Chemical Science Vol -1

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Content Provider	Royal Society of Chemistry (RSC)
Author	Perras, Frédéric A. Bryce, David L.
Copyright Year	2014
Abstract	Diboron compounds are a part of a relatively unexplored, yet immensely useful, class of compounds. Their main use is for β-boration reactions where a boron center is rendered nucleophilic with the use of a metal catalyst or a Lewis base (alkoxide, amine, or NHC) to form a sp2–sp3 diboron compound. The reactivity of these reagents is largely dictated by the nature of the B–B bond (strength and polarity); however, no experimental methods have been used to directly probe both of these quantities. We demonstrate that unprecedented experimental information regarding the B–B bond may be obtained using 11B solid-state NMR spectroscopy. For example, the 11B quadrupolar coupling constants can be understood on the basis of the polarization of the B–B bond. 11B double-quantum-filtered (DQF) J-resolved NMR spectroscopy was applied to easily and accurately measure J(11B,11B) coupling constants with high precision. These are shown to be well correlated with the orbital energy of the B–B σ-bonding natural bond orbital as well as the hybridisation states of the boron atoms in the bond. An increase in the p character of the bond by electron-donating ligands or via the formation of a sp2–sp3 diboron compound weakens the bond, increases the bond length, and decreases the J(11B,11B) coupling constants. These experiments provide a detailed experimental characterization of the B–B bond and may be useful in understanding the reactivity of diboron compounds and in designing new systems. The potential applicability of 11B DQF J-resolved NMR spectroscopy towards analyzing complex mixtures of diboron compounds and towards measuring 11B J coupling across multiple intervening bonds is also investigated and shows much promise.
Starting Page	2428
Ending Page	2437
Page Count	10
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	6
Journal	Chemical Science
DOI	10.1039/c4sc00603h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Lewis acids and bases Boron Solid-state nuclear magnetic resonance Covalent bond Alkoxide Nuclear magnetic resonance Natural bond orbital
Content Type	Text
Resource Type	Article
Subject	Chemistry

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

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Boron – boron J coupling constants are unique probes of electronic structure : a solid-state NMR and molecular orbital study

Spying on the boron–boron triple bond using spin–spin coupling measured from ¹¹B solid-state NMR spectroscopy

Structure elucidation of a complex CO₂-based organic framework material by NMR crystallography

Natural bond orbital/natural J-coupling study of vicinal couplings

Symmetry-Amplified J Splittings for Quadrupolar Spin Pairs: A Solid- State NMR Probe of Homoatomic Covalent Bonds

7Li solid-state NMR of lithium amides: structural information from 7Li quadrupolar coupling constants†

UNDERSTANDING DELOCALIZATION AND HYPERCONJUGATION IN TERMS OF (COVALENT AND IONIC) RESONANCE STRUCTURES

Solid-state NMR study of locations and dynamics of interlayer cationsand water in kanemite

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Similar Documents

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Boron – boron J coupling constants are unique probes of electronic structure : a solid-state NMR and molecular orbital study

Spying on the boron–boron triple bond using spin–spin coupling measured from 11B solid-state NMR spectroscopy

Structure elucidation of a complex CO2-based organic framework material by NMR crystallography

Natural bond orbital/natural J-coupling study of vicinal couplings

Symmetry-Amplified J Splittings for Quadrupolar Spin Pairs: A Solid- State NMR Probe of Homoatomic Covalent Bonds

7Li solid-state NMR of lithium amides: structural information from 7Li quadrupolar coupling constants†

UNDERSTANDING DELOCALIZATION AND HYPERCONJUGATION IN TERMS OF (COVALENT AND IONIC) RESONANCE STRUCTURES

Solid-state NMR study of locations and dynamics of interlayer cationsand water in kanemite

Boron–boron J coupling constants are unique probes of electronic structure: a solid-state NMR and molecular orbital study

Spying on the boron–boron triple bond using spin–spin coupling measured from ¹¹B solid-state NMR spectroscopy

Structure elucidation of a complex CO₂-based organic framework material by NMR crystallography