What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

Sai V. C. Vummaleti, David J. Nelson, Albert Poater, Adrian Gomez-Suarez, David B. Cordes, Alexandra M. Z. Slawin, Steven P. Nolan, Luigi Cavallo

Research output: Contribution to journalArticle

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Abstract

The electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the [small pi]-accepting ability of NHCs, independent of their [sigma]-donating ability, via the collection of 77Se or 31P NMR spectra, respectively. Herein, the synthesis and characterisation of selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that [small delta]Se is correlated to the energy gap between a filled lone pair orbital on Se and the empty [small pi]* orbital corresponding to the Se-NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital [sigma]-contribution to bonding and the chemical shielding, while a good correlation was found between the [small pi]-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept [small pi]-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between [small delta]Se and [small delta]P and [small pi]-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.
LanguageEnglish
Number of pages10
JournalChemical Science
Early online date2 Jan 2015
DOIs
Publication statusPublished - 2015

Fingerprint

Shielding
Nuclear magnetic resonance spectroscopy
Electronic properties
Coordination Complexes
Selenium
Carrier concentration
Energy gap
Metals
Nuclear magnetic resonance
Ligands
Decomposition
carbene
selenourea

Keywords

  • NMR spectroscopy
  • selenoureas
  • phosphinidenes

Cite this

Vummaleti, Sai V. C. ; Nelson, David J. ; Poater, Albert ; Gomez-Suarez, Adrian ; Cordes, David B. ; Slawin, Alexandra M. Z. ; Nolan, Steven P. ; Cavallo, Luigi. / What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?. In: Chemical Science. 2015.
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What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes? / Vummaleti, Sai V. C.; Nelson, David J.; Poater, Albert; Gomez-Suarez, Adrian; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.; Cavallo, Luigi.

In: Chemical Science, 2015.

Research output: Contribution to journalArticle

TY - JOUR

T1 - What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

AU - Vummaleti, Sai V. C.

AU - Nelson, David J.

AU - Poater, Albert

AU - Gomez-Suarez, Adrian

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Nolan, Steven P.

AU - Cavallo, Luigi

PY - 2015

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N2 - The electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the [small pi]-accepting ability of NHCs, independent of their [sigma]-donating ability, via the collection of 77Se or 31P NMR spectra, respectively. Herein, the synthesis and characterisation of selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that [small delta]Se is correlated to the energy gap between a filled lone pair orbital on Se and the empty [small pi]* orbital corresponding to the Se-NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital [sigma]-contribution to bonding and the chemical shielding, while a good correlation was found between the [small pi]-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept [small pi]-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between [small delta]Se and [small delta]P and [small pi]-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.

AB - The electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the [small pi]-accepting ability of NHCs, independent of their [sigma]-donating ability, via the collection of 77Se or 31P NMR spectra, respectively. Herein, the synthesis and characterisation of selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that [small delta]Se is correlated to the energy gap between a filled lone pair orbital on Se and the empty [small pi]* orbital corresponding to the Se-NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital [sigma]-contribution to bonding and the chemical shielding, while a good correlation was found between the [small pi]-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept [small pi]-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between [small delta]Se and [small delta]P and [small pi]-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.

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KW - phosphinidenes

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M3 - Article

JO - Chemical Science

T2 - Chemical Science

JF - Chemical Science

SN - 2041-6520

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