NDLI: Opening the black box of mixed-metal TMP metallating reagents: direct cadmation or lithium

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

Structure and biosynthesis of the unusual polyketide alkaloid coelimycin P1, a metabolic product of the cpk gene cluster of Streptomyces coelicolor M145

Azulene-based conjugated polymers: unique seven-membered ring connectivity leading to stimuli-responsiveness

Twice tied tight: Enforcing conformational order in bicyclic peptoid oligomers

On the mechanism of dynamic polymerization via recycled ss-DNA templated assembly of non-natural bases

What makes efficient circularly polarised luminescence in the condensed phase: aggregation-induced circular dichroism and light emission

The challenges of using a copper fluorescent sensor (CS1) to track intracellular distributions of copper in neuronal and glial cells

A highly selective ratiometric near-infrared fluorescent cyanine sensor for cysteine with remarkable shift and its application in bioimaging

Genetically encoded alkenyl–pyrrolysine analogues for thiol–ene reaction mediated site-specific protein labeling

Terrylene bisimide-diarylethene photochromic switch

Excitation energy migration in covalently linked perylene bisimide macrocycles

On the maximum bond multiplicity of carbon: unusual C≣U quadruple bonding in molecular CUO

Labelling of nucleosides and oligonucleotides by solvatochromic 4-aminophthalimide fluorophore for studying DNA–protein interactions

Crossed intermolecular [2 + 2] cycloaddition of styrenes by visible light photocatalysis

Transforming CdS into an efficient visible light photocatalyst for selective oxidation of saturated primary C–H bonds under ambient conditions

Vertex-directed self-assembly of a high symmetry supermolecular building block using a custom-designed porphyrin

A poly(ethylene glycol)-brush decorated magnetic polymer for highly specific enrichment of phosphopeptides

State-to-state differential cross-sections for the reactive scattering of H^*(n) with o-D₂

A new, centered 32-electron system: the predicted [U@Si₂₀]⁶⁻-like isoelectronic series

A chemical synthesis of 11-methoxy mitragynine pseudoindoxyl featuring the interrupted Ugi reaction

Copper-catalyzed decarboxylative alkenylation of sp³ C–H bonds with cinnamic acids via a radical process

Gold meets enamine catalysis in the enantioselective α-allylic alkylation of aldehydes with alcohols

Promoted activity of Cr(Salen) in a nanoreactor for kinetic resolution of terminal epoxides

Hysteresis in the ground and excited spin state up to 10 T of a [Mn^III₆Mn^III]³⁺ triplesalen single-molecule magnet

Back cover

Chemical Science Vol - 3 Issue - 8

Chemical Science Vol - 3 Issue - 7

Chemical Science Vol - 3 Issue - 6

Chemical Science Vol - 3 Issue - 5

Chemical Science Vol - 3 Issue - 4

Chemical Science Vol - 3 Issue - 3

Chemical Science Vol - 3 Issue - 2

Chemical Science Vol -2

Chemical Science Vol -1

Opening the black box of mixed-metal TMP metallating reagents: direct cadmation or lithium–cadmium transmetallation?

Content Provider	Royal Society of Chemistry (RSC)
Author	Mulvey, Robert E. Armstrong, David R. Parkinson, John A. Kennedy, Alan R. Robertson, Stuart D.
Copyright Year	2012
Abstract	Designed to remove some of the mystery surrounding mixed-metal TMP (2,2,6,6-tetramethylpiperidide) metallating reagents, this study examines in detail “LiCd(TMP)3” in its own right. Previously established as an excellent “cadmating” (Cd–H exchange) reagent towards a wide variety of aromatic substrates, “LiCd(TMP)3” has been investigated by 1H, 13C and 113Cd NMR studies as well as by DOSY NMR spectroscopy. This evidence puts a question mark against its ate formulation implying it exists in THF solution as two independent homometallic amides. Exploring the reactivity of “LiCd(TMP)3” with anisole as a test substrate, both experimentally by NMR studies and theoretically by DFT studies suggests a two-step lithiation/transmetallation process in which the initially formed ortho-lithiated species undergoes a reaction with Cd(TMP)2 to form new Cd-C and Li–N bonds. For completeness, the homometallic cadmium component Cd(TMP)2 has been comprehensively characterised for the first time including a crystal structure determination revealing a near-linear N–Cd–N arrangement.
Starting Page	2700
Ending Page	2707
Page Count	8
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	3
Issue Number	9
Journal	Chemical Science
DOI	10.1039/c2sc20392h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Cadmium THF TMP Anisole Nuclear magnetic resonance spectroscopy Li Reagent Transmetalation
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

TMP (2,2,6,6-tetramethylpiperidide)-aluminate bases: lithium-mediated alumination or lithiation–alkylaluminium-trapping reagents?

The insulator-metal transition upon lithium deintercalation from LiCoO2: electronic properties and 7Li NMR study

Li_0.6[Li_0.2Sn_0.8S₂] – a layered lithium superionic conductor

Use of mixed Li/K metal TMP amide (LiNK chemistry) for the synthesis of [2.2]metacyclophanes

A non-chiral lithium aluminate reagent for the determination of enantiomeric excess of chiral alcohols

A Nuclear Magnetic Resonance Spectroscopic Technique for the Characterization of Lithium Ion Pair Structures in THF and THF / HMPA Solution 1

Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record ⁷Li NMR shifts

Direct observation of a lithiated oxirane: a synergistic study using spectroscopic, crystallographic, and theoretical methods on the structure and stereodynamics of lithiated ortho-trifluoromethyl styrene oxide

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries

Opening the black box of mixed-metal TMP metallating reagents: direct cadmation or lithium–cadmium transmetallation?

Similar Documents

TMP (2,2,6,6-tetramethylpiperidide)-aluminate bases: lithium-mediated alumination or lithiation–alkylaluminium-trapping reagents?

The insulator-metal transition upon lithium deintercalation from LiCoO2: electronic properties and 7Li NMR study

Li0.6[Li0.2Sn0.8S2] – a layered lithium superionic conductor

Use of mixed Li/K metal TMP amide (LiNK chemistry) for the synthesis of [2.2]metacyclophanes

A non-chiral lithium aluminate reagent for the determination of enantiomeric excess of chiral alcohols

A Nuclear Magnetic Resonance Spectroscopic Technique for the Characterization of Lithium Ion Pair Structures in THF and THF / HMPA Solution 1

Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record 7Li NMR shifts

Direct observation of a lithiated oxirane: a synergistic study using spectroscopic, crystallographic, and theoretical methods on the structure and stereodynamics of lithiated ortho-trifluoromethyl styrene oxide

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li2O2—the discharge product in lithium-air batteries

Opening the black box of mixed-metal TMP metallating reagents: direct cadmation or lithium–cadmium transmetallation?

Li_0.6[Li_0.2Sn_0.8S₂] – a layered lithium superionic conductor

Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations, unique structures and record ⁷Li NMR shifts

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries