Rare Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic OlefinCitation formats

  • External authors:
  • John Seed
  • Matthew Gregson
  • Ashley Wooles

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Rare Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic Olefin. / Liddle, Stephen; Seed, John; Gregson, Matthew; Tuna, Floriana; Chilton, Nicholas; Wooles, Ashley; Mcinnes, Eric.

In: Angewandte Chemie - International Edition, 2017.

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@article{32176c47fefd4c0d814e6d9d0c5a8bf8,
title = "Rare Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic Olefin",
abstract = "Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found only in the free form or ligated to a few d-block ions. Here, we report unprecedented f-block MIC complexes [M(N'')3{CN(Me)C(Me)N(Me)CH}] (M = U, Y, La, Nd; N'' = N(SiMe3)2). These complexes were prepared by a formal 1,4-proton migration reaction when the metal-triamides [M(N'')3] were treated with the N-heterocyclic olefin H2C=C(NMeCH)2, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f3 uranium(III) complex suggest the presence of a U=C donor-acceptor bond, composed of a MIC→U σ-component and a U(5f)→MIC(2p) π-back-bond, but for the d0f0 Y and La and 4f3 Nd congeners only MIC→M σ-bonding is found. Considering the generally negligible π-acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognising MICs as potential π-acid ligands when coordinated to reducing metals.",
author = "Stephen Liddle and John Seed and Matthew Gregson and Floriana Tuna and Nicholas Chilton and Ashley Wooles and Eric Mcinnes",
year = "2017",
doi = "10.1002/ange.201706546",
language = "English",
journal = "Angewandte Chemie, International Edition",
issn = "1433-7851",
publisher = "John Wiley & Sons Ltd",

}

RIS

TY - JOUR

T1 - Rare Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic Olefin

AU - Liddle, Stephen

AU - Seed, John

AU - Gregson, Matthew

AU - Tuna, Floriana

AU - Chilton, Nicholas

AU - Wooles, Ashley

AU - Mcinnes, Eric

PY - 2017

Y1 - 2017

N2 - Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found only in the free form or ligated to a few d-block ions. Here, we report unprecedented f-block MIC complexes [M(N'')3{CN(Me)C(Me)N(Me)CH}] (M = U, Y, La, Nd; N'' = N(SiMe3)2). These complexes were prepared by a formal 1,4-proton migration reaction when the metal-triamides [M(N'')3] were treated with the N-heterocyclic olefin H2C=C(NMeCH)2, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f3 uranium(III) complex suggest the presence of a U=C donor-acceptor bond, composed of a MIC→U σ-component and a U(5f)→MIC(2p) π-back-bond, but for the d0f0 Y and La and 4f3 Nd congeners only MIC→M σ-bonding is found. Considering the generally negligible π-acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognising MICs as potential π-acid ligands when coordinated to reducing metals.

AB - Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found only in the free form or ligated to a few d-block ions. Here, we report unprecedented f-block MIC complexes [M(N'')3{CN(Me)C(Me)N(Me)CH}] (M = U, Y, La, Nd; N'' = N(SiMe3)2). These complexes were prepared by a formal 1,4-proton migration reaction when the metal-triamides [M(N'')3] were treated with the N-heterocyclic olefin H2C=C(NMeCH)2, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f3 uranium(III) complex suggest the presence of a U=C donor-acceptor bond, composed of a MIC→U σ-component and a U(5f)→MIC(2p) π-back-bond, but for the d0f0 Y and La and 4f3 Nd congeners only MIC→M σ-bonding is found. Considering the generally negligible π-acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognising MICs as potential π-acid ligands when coordinated to reducing metals.

U2 - 10.1002/ange.201706546

DO - 10.1002/ange.201706546

M3 - Article

JO - Angewandte Chemie, International Edition

JF - Angewandte Chemie, International Edition

SN - 1433-7851

ER -