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HurdlingOxoWall SIGNED

Late First-Row Transition Metal-Oxo Complexes for C–H Bond Activation

Total Cost €

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EC-Contrib. €

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Partnership

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 HurdlingOxoWall project word cloud

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industries    ambient    accomplished    lm    coordinate    oxo    poorly    force    investigations    oxidant    chemical    hydrocarbons    route    green    chemicals    nature    oxidation    rarr    materials    potent    heavily    catalysing    stabilisation    thermodynamic    oil    inert    ch4    modern    reactive    strongest    hydrocarbon    stocks    cat    significantly    oxidatively       co    count    metal    designing    considerable    acquired    display    activation    reactivity    complexes    transition    commodity    species    ch3oh    prior    manipulated    ligands    feed    potentially    molecular    row    prepare    cheap    powerful    em    electron    catalytic    sustainable    catalysts    activate    first    natural    activated    family    unprecedented    gas    preparing    remarkably    bonds    temperature    inspired    thermodynamics    thoroughly    ni    catalyst    interrogate    oxidative    active    cu    rely    generation    functionalisation    contain    driving    pharmaceutical    guide    saturated    compounds   

Project "HurdlingOxoWall" data sheet

The following table provides information about the project.

Coordinator
THE PROVOST, FELLOWS, FOUNDATION SCHOLARS & THE OTHER MEMBERS OF BOARD OF THE COLLEGE OF THE HOLY & UNDIVIDED TRINITY OF QUEEN ELIZABETH NEAR DUBLIN 

Organization address
address: College Green
city: DUBLIN
postcode: 2
website: www.tcd.ie

contact info
title: n.a.
name: n.a.
surname: n.a.
function: n.a.
email: n.a.
telephone: n.a.
fax: n.a.

 Coordinator Country Ireland [IE]
 Project website http://chemistry.tcd.ie/staff/people/mcdonald
 Total cost 1˙499˙865 €
 EC max contribution 1˙499˙865 € (100%)
 Programme 1. H2020-EU.1.1. (EXCELLENT SCIENCE - European Research Council (ERC))
 Code Call ERC-2015-STG
 Funding Scheme ERC-STG
 Starting year 2016
 Duration (year-month-day) from 2016-03-01   to  2021-02-28

 Partnership

Take a look of project's partnership.

# participants  country  role  EC contrib. [€] 
1    THE PROVOST, FELLOWS, FOUNDATION SCHOLARS & THE OTHER MEMBERS OF BOARD OF THE COLLEGE OF THE HOLY & UNDIVIDED TRINITY OF QUEEN ELIZABETH NEAR DUBLIN IE (DUBLIN) coordinator 1˙499˙865.00

Map

 Project objective

The chemical, pharmaceutical, and materials industries rely heavily upon chemicals from oil and natural gas feed-stocks (saturated hydrocarbons) that require considerable functionalisation prior to use. Catalytic oxidative functionalisation (e.g. CH4 [O] cat. → CH3OH), using first row transition metal catalysts, is potentially a sustainable, cheap, and green route to these high-commodity chemicals. However, catalytic oxidation remains a great modern challenge because such hydrocarbons contain remarkably strong inert C–H bonds that can only be activated with potent catalysts. We will take a Nature-inspired approach to designing and preparing powerful oxidation catalysts: we will interrogate the active oxidant, a metal-oxo (M=O) species, to guide our catalyst design. Specifically, we will prepare unprecedented Late first-row transition Metal-Oxo complexes (LM=O’s, LM = Co, Ni, Cu) that will activate the strongest of C–H bonds (e.g. CH4).

This will be accomplished using a family of novel low coordinate ligands that will support LM=O’s. Due to their expected potent reactivity we will prepare LM=O’s under unique oxidatively robust, low-temperature conditions to ensure their stabilisation. The poorly understood factors (thermodynamics, metal, d-electron count) that control the reactivity of M=O’s will be thoroughly investigated. Based on these investigations LM=O reactivity will be manipulated and optimised. We expect LM=O’s will be significantly more reactive than any early transition metal-oxo’s (EM=O’s), because they will display a greater thermodynamic driving force for C–H activation. It is thus expected that LM=O’s will be capable of the activation of the strongest of C–H bonds (i.e. CH4). Driven by the knowledge acquired from these investigations, we will design and prepare the next generation of molecular oxidation catalysts - a family of late first-row transition metal compounds capable of catalysing hydrocarbon functionalisation under ambient conditions.

 Publications

year authors and title journal last update
List of publications.
2016 Paolo Pirovano, Erik R. Farquhar, Marcel Swart, and Aidan R. McDonald
Tuning the Reactivity of Terminal Nickel(III)–Oxygen Adducts for C–H Bond Activation
published pages: , ISSN: 0002-7863, DOI: 10.1021/jacs.6b08406
Journal of the American Chemical Society 2019-07-08
2016 Andrew D. Ure, Isabel Abánades Lázaro, Michelle Cotter, Aidan R. McDonald
Synthesis and characterisation of a mesocyclic tripodal triamine ligand
published pages: , ISSN: 1477-0520, DOI: 10.1039/C5OB01556A
Organic and Biomolecular Chemistry 2019-07-08
2018 Paolo Pirovano, Abigail R. Berry, Marcel Swart, Aidan R. McDonald
Indirect evidence for a Ni III –oxyl oxidant in the reaction of a Ni II complex with peracid
published pages: 246-250, ISSN: 1477-9226, DOI: 10.1039/C7DT03316H
Dalton Transactions 47/1 2019-04-16
2018 Paolo Pirovano, Aidan R. McDonald
Synthetic High-Valent M-O-X Oxidants
published pages: 547-560, ISSN: 1434-1948, DOI: 10.1002/ejic.201701072
European Journal of Inorganic Chemistry 2018/5 2019-04-16
2018 Paolo Pirovano, Brendan Twamley, Aidan R. McDonald
Modulation of Nickel Pyridinedicarboxamidate Complexes to Explore the Properties of High-valent Oxidants
published pages: 5238-5245, ISSN: 0947-6539, DOI: 10.1002/chem.201704618
Chemistry - A European Journal 24/20 2019-04-16
2018 Prasenjit Mondal, Paolo Pirovano, Ankita Das, Erik R. Farquhar, Aidan R. McDonald
Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex
published pages: 1834-1841, ISSN: 0002-7863, DOI: 10.1021/jacs.7b11953
Journal of the American Chemical Society 140/5 2019-04-16

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