'Inverse' Coordination: A New Design Concept in Supramolecular Inorganic Chemistry
Lead Research Organisation:
University of Strathclyde
Department Name: Pure and Applied Chemistry
Abstract
While organic hosts for the coordination of anions have been extensively studied in the past few decades, studies of inorganic counterparts (whose frameworks are based predominantly on non-carbon atoms) have been much rarer. Indeed, the potentially general usefulness of inorganic systems of this type in anion coordination and supramolecular chemistry has not been realised, despite the fact that inorganic hosts frequently offer far greater affinity for anions than organic relatives (particularly those containing Lewis acidic metal atoms). In establishing a new collaboration, this proposal seeks to harness the expertise of two of the UK's leading researchers in main group chemistry in the development and exploitation of the new synthetic concept of inverse coordination of salt lattices, in which a range of elegant metal-based acceptors will be used as anion hosts. A major area of interest is the rational design of supramolecular main group assemblies using the concept of inverse coordination. In addition to providing the means for the stabilisation of unusual inorganic and organometallic anions, the immobilisation of the anions of simple salts by metal-based inverse ligands provides a novel approach to fast-ion conductors.
Organisations
Publications
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Alberola A
(2009)
Bis[(trimethylsilyl)methyl]manganese: Structural Variations of Its Solvent-Free and TMEDA-, Pyridine-, and Dioxane-Complexed Forms
in Organometallics
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Alborés P
(2009)
Direct C-H metalation with chromium(II) and iron(II): transition-metal host/benzenediide guest magnetic inverse-crown complexes.
in Angewandte Chemie (International ed. in English)
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Armstrong D
(2010)
Diisopropylamide and TMP Turbo-Grignard Reagents: A Structural Rationale for their Contrasting Reactivities
in Angewandte Chemie
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Armstrong DR
(2010)
Diisopropylamide and TMP turbo-Grignard reagents: a structural rationale for their contrasting reactivities.
in Angewandte Chemie (International ed. in English)
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Balloch L
(2010)
Structural elaboration of the surprising ortho-zincation of benzyl methyl ether.
in Chemical communications (Cambridge, England)
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Balloch L
(2009)
Structural variations within group 1 (Li-Cs)+ (2,2,6,6-tetramethyl-1-piperidinyloxy)- complexes made via metallic reduction of the nitroxyl radical.
in Inorganic chemistry
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Blair VL
(2008)
Tuning the basicity of synergic bimetallic reagents: switching the regioselectivity of the direct dimetalation of toluene from 2,5- to 3,5-positions.
in Angewandte Chemie (International ed. in English)
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Blair VL
(2009)
Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(II) of ferrocene.
in Chemistry (Weinheim an der Bergstrasse, Germany)
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Blair VL
(2008)
Structural complexity of the magnesiation of furan: an octadecanuclear product with a subporphyrin-like Mg3(2,5-fur-di-yl)3 substructure.
in Chemical communications (Cambridge, England)
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Blair VL
(2008)
Alkali-metal-mediated manganationII of functionalized arenes and applications of ortho-manganated products in Pd-catalyzed cross-coupling reactions with iodobenzene.
in Chemistry (Weinheim an der Bergstrasse, Germany)
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Blair VL
(2009)
Alkali-metal-mediated manganation(II) of naphthalenes: constructing metalla-anthracene and metalla-phenanthrene structures.
in Inorganic chemistry
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Campbell R
(2010)
cis-2,6-Dimethylpiperidide: a structural mimic for TMP (2,2,6,6-tetramethylpiperidide) or DA (diisopropylamide)?
in Dalton transactions (Cambridge, England : 2003)
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Carrella L
(2010)
Synthesis and Structure of a Potassium Potassiochromate: A Bis-Chromium(II) Molecule Held Together by Near-Square-Planar Potassium-Ligand Bridges
in Organometallics
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Carrella LM
(2007)
Sodium-mediated manganation: direct mono- and dimanganation of benzene and synthesis of a transition-metal inverse-crown complex.
in Angewandte Chemie (International ed. in English)
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Clegg W
(2011)
Synthesis and Structures of [(Trimethylsilyl)methyl]sodium and -potassium with Bi- and Tridentate N-Donor Ligands
in European Journal of Inorganic Chemistry
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Clegg W
(2009)
Structurally Defined Potassium-Mediated Zincation of Pyridine and 4-R-Substituted Pyridines (R=Et, i Pr, t Bu, Ph, and Me 2 N) by Using Dialkyl-TMP-Zincate Bases
in Chemistry - A European Journal
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Clegg W
(2009)
Structural tracking of the potassium-mediated magnesiation of anisole.
in Chemistry (Weinheim an der Bergstrasse, Germany)
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Clegg W
(2009)
Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole: experimental evidence of amido basicity and structural elucidation of key reaction intermediates.
in Journal of the American Chemical Society
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Clegg W
(2010)
Potassium-mediated zincation of ferrocene and ruthenocene: potassium, the architect behind supramolecular structural variations.
in Dalton transactions (Cambridge, England : 2003)
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Conway B
(2007)
Structurally-defined direct C-magnesiation and C-zincation of N-heterocyclic aromatic compounds using alkali-metal-mediated metallation.
in Chemical communications (Cambridge, England)
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Conway B
(2010)
Structural insights into mono-amido tris-alkyl potassium aluminates
in New Journal of Chemistry
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Conway B
(2007)
Isolation and structural elucidation of a key aluminoaromatic intermediate and evidence for dismutation phenomena in TMP-alumination chemistry.
in Chemical communications (Cambridge, England)
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Conway B
(2010)
Structurally stimulated deprotonation/alumination of the TMP anion.
in Angewandte Chemie (International ed. in English)
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Conway B
(2008)
Structurally-defined potassium-mediated regioselective zincation of amino- and alkoxy-substituted pyridines.
in Chemical communications (Cambridge, England)
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Conway B
(2009)
Contacted Ion-Pair Lithium Alkylamidoaluminates: Intramolecular Alumination (Al-H Exchange) Traps for TMEDA and PMDETA
in Organometallics
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Crosbie E
(2010)
Structurally engineered deprotonation/alumination of THF and THTP with retention of their cycloanionic structures.
in Angewandte Chemie (International ed. in English)
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Forret R
(2010)
Multistep Self-Assembly of Heteroleptic Magnesium and Sodium-Magnesium Benzamidinate Complexes
in Organometallics
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Garcia-Alvarez J
(2007)
Alkali-metal-mediated manganation: a method for directly attaching manganese(II) centers to aromatic frameworks.
in Angewandte Chemie (International ed. in English)
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García-Alvarez J
(2007)
Lewis base stabilized lithium TMP-aluminates: an unexpected fragmentation and capture reaction involving cyclic ether 1,4-dioxane.
in Chemical communications (Cambridge, England)
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García-Alvarez P
(2008)
Unmasking representative structures of TMP-active Hauser and turbo-Hauser bases.
in Angewandte Chemie (International ed. in English)
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Garden JA
(2011)
Neutral zinc, lower-order zincate and higher-order zincate derivatives of pyrrole: synthesis and structural characterisation of zinc complexes with one, two, three or four pyrrolyl ligands.
in Dalton transactions (Cambridge, England : 2003)
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Kennedy A
(2009)
Structural Elucidation of tmeda-Solvated Alkali Metal Diphenylamide Complexes
in European Journal of Inorganic Chemistry
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Kennedy AR
(2010)
N-Heterocyclic carbene stabilized adducts of alkyl magnesium amide, bisalkyl magnesium and Grignard reagents: trapping oligomeric organo s-block fragments with NHCs.
in Dalton transactions (Cambridge, England : 2003)
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Kennedy AR
(2008)
Manganese(II)-lithium and -sodium inverse crown ether (ICE) complexes.
in Chemical communications (Cambridge, England)
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Kennedy AR
(2010)
Lithium and aluminium carbamato derivatives of the utility amide 2,2,6,6-tetramethylpiperidide.
in Dalton transactions (Cambridge, England : 2003)
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Kennedy AR
(2009)
Synergic sedation of sensitive anions: alkali-mediated zincation of cyclic ethers and ethene.
in Science (New York, N.Y.)
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Mulvey R
(2010)
Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran
in Nature Chemistry
Description | This project was exceptionally productive leading to the publication of 18 high impact papers in international journals. Key advances were made in synergistic synthesis where two metal reagents can perform chemical reactions outside the scope of the single metal reagents from which they are composed. The impact of these findings can be evidenced by the fact that breakthroughs on sodium-zinc and potassium-zinc synergistic systems were published in the leading world class journal "Science". Specifically it was shown that cyclic ethers could be controllably metallated by these bimetallic compositions and sedated from ring opening which occurs invariably when these cyclic ethers are deprotonated by conventional single metal based organometallic reagents. These deprotonated ethers can then be employed in synthetic campaigns. Aside from fundamental interest, this work stimulated interest from the pharmaceutical industry with AstraZeneca sponsoring a future PhD studentship in the bimetallic area. |
Exploitation Route | The results obtained could be useful to synthetic chemists in both organic and inorganic chemistry. |
Sectors | Chemicals Pharmaceuticals and Medical Biotechnology |
Description | AstraZeneca |
Amount | £24,000 (GBP) |
Funding ID | 115522 |
Organisation | AstraZeneca |
Sector | Private |
Country | United Kingdom |
Start | 09/2011 |
End | 09/2014 |
Description | Invite Lecture Ludwig-Maximilians Universität, Munich, Germany. |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Invited lecture |
Year(s) Of Engagement Activity | 2008 |
Description | Invite Lectures in Germany at Universität Karlsruhe (TH), Johann Wolfgang Goethe-Universität, Frankfurt, University of Göttingen |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | A series of invited lectures across Germany |
Year(s) Of Engagement Activity | 2009 |
Description | Invited presentation 235th American Chemical Society National Meeting, New Orleans, Louisiana, USA. |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Invited lecture |
Year(s) Of Engagement Activity | 2008 |
Description | Keynote lecture at the 42nd IUPAC Congress, Glasgow, UK |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Invite plenary lecture at a world leading conference |
Year(s) Of Engagement Activity | 2009 |
Description | New Chemistry of the Elements Symposium, Royal Society London, 2008 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Invited lecture |
Year(s) Of Engagement Activity | 2008 |
Description | Plenary Lecture at ICHAC-9, Universidad de Oviedo, Spain. |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Plenary lecture at an international conference. |
Year(s) Of Engagement Activity | 2009 |
Description | Zing Main Group Chemistry Conference, Playa del Carmen, Mexico |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Plenary lecture at an international conference. |
Year(s) Of Engagement Activity | 2009 |