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HurdlingOxoWall SIGNED

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

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EC-Contrib. €

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Partnership

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 HurdlingOxoWall project word cloud

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

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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