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Entangled pincer ligand architectures and their application in the transition-metal-mediated activation of alkanes

Total Cost €


EC-Contrib. €






 ENTANGLED-TM-ALKANE project word cloud

Explore the words cloud of the ENTANGLED-TM-ALKANE project. It provides you a very rough idea of what is the project "ENTANGLED-TM-ALKANE" about.

difficult    selective       reactions    entangled    alkanes    inspired    macromolecules    assemblies    systematic    transition    close    interaction    activation    ranging    bond    intermediates    tridentate    chemistry    petroleum    transient    homogeneous    systematically    pivotal    macrocycle    gap    adducts    quantitative    nature    foundation    macrocyclic    implications    transformation    potentially    ligands    tm    supramolecular    circumvented    metals    proven    previously    catenanes    dissociation    centres    synthetic    outlines    synthesis    geometry    ultimately    donors    nominally    exceedingly    supporting    containing    reactive    structure    metal    formed    innovative    organic    body    interwoven    organometallic    area    unprecedented    pincer    mechanically    relationships    rotaxanes    probed    reaction    variation    components    topology    interlocked    mechanical    powerful    isolation    fundamental    complexes    interacting    sigma    contemporary    alkane    preparation    entanglement    qualitative    compile    substrates    definitive    catalysis    intact    proximity    extremely    centre   

Project "ENTANGLED-TM-ALKANE" data sheet

The following table provides information about the project.


Organization address
address: Kirby Corner Road - University House
postcode: CV4 8UW

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 United Kingdom [UK]
 Project website
 Total cost 1˙521˙137 €
 EC max contribution 1˙521˙137 € (100%)
 Programme 1. H2020-EU.1.1. (EXCELLENT SCIENCE - European Research Council (ERC))
 Code Call ERC-2014-STG
 Funding Scheme ERC-STG
 Starting year 2015
 Duration (year-month-day) from 2015-04-01   to  2020-03-31


Take a look of project's partnership.

# participants  country  role  EC contrib. [€] 
1    THE UNIVERSITY OF WARWICK UK (COVENTRY) coordinator 1˙521˙137.00


 Project objective

The selective transformation of alkanes is an area of contemporary importance with wide-ranging implications for organic synthesis and the effective use of petroleum resources. While homogeneous transition metal catalysis is a potentially powerful means for achieving this objective, the fundamental organometallic chemistry of alkane activation reactions has proven to be exceedingly difficult to investigate due to the weakly interacting nature of alkanes. To address this knowledge gap and provide the foundation for future advancement of the field, ENTANGLED-TM-ALKANE outlines a systematic approach for the study of pivotal sigma–alkane complex intermediates; nominally transient and extremely reactive metal-alkane adducts formed through coordination of an intact C–H bond to the metal centre. Inspired from supramolecular chemistry, the approach involves the innovative use of systems containing alkane substrates held in close proximity to reactive metal centres through mechanical entanglement within supporting tridentate macrocyclic ‘pincer’ ligands (i.e. alkane based [2]rotaxanes and [2]catenanes). Through the interwoven topology of these systems, problematic dissociation reactions of sigma–alkane complexes will be circumvented, facilitating isolation and ultimately enabling their structure and reaction chemistry to be probed in much greater detail than has been previously possible. The project objectives are to: (a) develop and use new synthetic (supramolecular) methodologies for the preparation of these mechanically interlocked metal-alkane assemblies; (b) systematically investigate the organometallic chemistry of the metal centre and its interaction with the entangled alkane; and through variation of the macromolecules’ components (macrocycle donors and geometry, alkane, metal), (c) compile a definitive and unprecedented body of qualitative and quantitative structure-activity relationships for the activation alkanes using transition metals.


year authors and title journal last update
List of publications.
2019 Matthew R. Gyton, Baptiste Leforestier, Adrian B. Chaplin
Rhodium(I) Pincer Complexes of Nitrous Oxide
published pages: 15295-15298, ISSN: 1433-7851, DOI: 10.1002/anie.201908333
Angewandte Chemie International Edition 58/43 2020-04-09
2019 Gemma L. Parker, Samantha Lau, Baptiste Leforestier, Adrian B. Chaplin
Probing the Donor Properties of Pincer Ligands Using Rhodium Carbonyl Fragments: An Experimental and Computational Case Study
published pages: 3791-3798, ISSN: 1434-1948, DOI: 10.1002/ejic.201900727
European Journal of Inorganic Chemistry 2019/33 2020-04-09
2019 Matthew R. Gyton, Thomas M. Hood, Adrian B. Chaplin
A convenient method for the generation of {Rh(PNP)} + and {Rh(PONOP)} + fragments: reversible formation of vinylidene derivatives
published pages: 2877-2880, ISSN: 1477-9226, DOI: 10.1039/c8dt05049j
Dalton Transactions 48/9 2020-04-09
2019 Thomas M. Hood, Baptiste Leforestier, Matthew R. Gyton, Adrian B. Chaplin
Synthesis and Structural Dynamics of Five-Coordinate Rh(III) and Ir(III) PNP and PONOP Pincer Complexes
published pages: 7593-7601, ISSN: 0020-1669, DOI: 10.1021/acs.inorgchem.9b00957
Inorganic Chemistry 58/11 2020-04-09
2018 Samantha L. Apps, Rhiannon E. Alflatt, Baptiste Leforestier, Caroline M. Storey, Adrian B. Chaplin
Divergent stereoisomers of molybdenum carbonyl complexes of NHC-based pincer ligands
published pages: 57-61, ISSN: 0277-5387, DOI: 10.1016/j.poly.2017.08.001
Polyhedron 143 2020-04-09
2017 Jack Emerson-King, Richard C. Knighton, Matthew R. Gyton, Adrian B. Chaplin
Rotaxane synthesis exploiting the M( i )/M( iii ) redox couple
published pages: 11645-11655, ISSN: 1477-9226, DOI: 10.1039/c7dt02648j
Dalton Transactions 46/35 2020-04-09
2018 Matthew R. Gyton, Baptiste Leforestier, Adrian B. Chaplin
Rhodium(III) and Iridium(III) Complexes of a NHC-Based Macrocycle: Persistent Weak Agostic Interactions and Reactions with Dihydrogen
published pages: 3963-3971, ISSN: 0276-7333, DOI: 10.1021/acs.organomet.8b00595
Organometallics 37/21 2020-04-09
2018 Caroline M. Storey, Matthew R. Gyton, Rhiann E. Andrew, Adrian B. Chaplin
Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching
published pages: 12003-12006, ISSN: 1433-7851, DOI: 10.1002/anie.201807028
Angewandte Chemie International Edition 57/37 2020-04-09
2016 Rhiann E. Andrew, Caroline M. Storey, Adrian B. Chaplin
Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles
published pages: 8937-8944, ISSN: 1477-9226, DOI: 10.1039/c6dt01263a
Dalton Trans. 45/21 2020-04-09

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