Si-O Elimination for the Generation of Heteronuclear Metal-Metal Bonds
Lead Research Organisation:
University of Bath
Department Name: Chemistry
Abstract
Compounds containing metal-metal bonds have attracted extensive interest over the last four decades. These compounds are fascinating and potentially useful owing to their ability to react with numerous small molecules of significance to areas such as sustainability and energy technologies (i.e. hydrogen, carbon dioxide). Current methods to access metal-metal bonds apply dangerous alkali metal reagents and are unselective precluding access to heteronuclear metal-metal bonds.
This research will seek to rationally synthesise Main Group and Transition Metal species containing hitherto unprecedented metal-metal bonding via the elimination of strong Si-O bonds.
Initially the work will focus on the generation of novel Main Group silyl compounds generated by sigma-bond metathesis applying known Main Group metal alkoxides. With a library of silyls generated their reactivity, most notably with Main Group and Transition Metal alkoxides, will be investigated.
With a validated methodology to access heteronuclear metal-metal bonds via Si-O elimination in hand, this method will be applied to a much wider range of metals and to alternative ligand systems to access low-coordinate species containing metal-metal bonds.
This research will seek to rationally synthesise Main Group and Transition Metal species containing hitherto unprecedented metal-metal bonding via the elimination of strong Si-O bonds.
Initially the work will focus on the generation of novel Main Group silyl compounds generated by sigma-bond metathesis applying known Main Group metal alkoxides. With a library of silyls generated their reactivity, most notably with Main Group and Transition Metal alkoxides, will be investigated.
With a validated methodology to access heteronuclear metal-metal bonds via Si-O elimination in hand, this method will be applied to a much wider range of metals and to alternative ligand systems to access low-coordinate species containing metal-metal bonds.
Organisations
People |
ORCID iD |
| Thomas HORSLEY DOWNIE (Student) |
Publications
Horsley Downie TM
(2020)
The first ring-expanded NHC-copper(i) phosphides as catalysts in the highly selective hydrophosphination of isocyanates.
in Chemical communications (Cambridge, England)
Horsley Downie TM
(2021)
A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes.
in Dalton transactions (Cambridge, England : 2003)
Studentship Projects
| Project Reference | Relationship | Related To | Start | End | Student Name |
|---|---|---|---|---|---|
| EP/N509589/1 | 30/09/2016 | 29/09/2021 | |||
| 1940084 | Studentship | EP/N509589/1 | 30/09/2017 | 29/09/2021 | Thomas HORSLEY DOWNIE |
| Description | The reactivity of a series of copper alkoxide complexes which are well-established in the literature has been investigated for novel catalytic application. Through careful design of experiment it was discovered that phosphorus-element bonds could be generated catalytically, mediated by these copper alkoxide complexes. A series of novel copper phosphide complexes were synthesised. The reactivity of the these complexes were investigated. It was they discovered they could be used to catalytically generate a rarely-reported class organophosphorus compounds in a highly atom-efficient manner. Copper boryl complexes are important intermediates in organometallic catalysis but are typically of limited stability. A stable copper boryl complex was synthesised and characterised. The reactivity of this complex with organic electrophiles was investigated, which resulted in a series of novel organometallic compounds that were characterised. |
| Exploitation Route | Outcomes of this funding include the catalytic generation of uncommon classes of organophosphorus compounds and the investigation into the synthesis and reactivity of novel copper(I) main group complexes. Organophosphorus compounds have extensive commerical applications, and these discoveries contribute to the development of economic routes to this class of chemicals. The investigations into the reactivity of new organometallic complexes potentially opens new synthetic pathways to compounds that can be adapted into catalytic routes to organic compounds which find use in academia and industry. |
| Sectors | Chemicals |