'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.

Publications

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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 (2010) Structurally stimulated deprotonation/alumination of the TMP anion. in Angewandte Chemie (International ed. in English)

 
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