University of Jyväskylä | JYX Digital Repository

  • English  | Give feedback |
    • suomi
    • English
 
  • Login
JavaScript is disabled for your browser. Some features of this site may not work without it.
View Item 
  • JYX
  • Artikkelit
  • Matemaattis-luonnontieteellinen tiedekunta
  • View Item
JYX > Artikkelit > Matemaattis-luonnontieteellinen tiedekunta > View Item

Electronic Structures of Main-Group Carbene Analogues

ThumbnailFinal Draft
View/Open
971.7 Kb

Downloads:  
Show download detailsHide download details  
Tuononen, H., Roesler, R., Dutton, J., & Ragogna, P. (2007). Electronic Structures of Main-Group Carbene Analogues. Inorganic Chemistry, 46(25), 10693-10706. https://doi.org/10.1021/ic701350e
Published in
Inorganic Chemistry
Authors
Tuononen, Heikki |
Roesler, Roland |
Dutton, Jason |
Ragogna, Paul
Date
2007
Discipline
Epäorgaaninen ja analyyttinen kemiaInorganic and Analytical Chemistry
Copyright
© 2007 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.

 
The electronic structures of 15 group 13−16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for the parent N-heterocyclic carbene (NHC), imidazol-2-ylidene. The results of this study present a uniform analysis of the similarities and differences in the electronic structures of p-block main-group carbene analogues. Though all systems are formally isovalent, the theoretical analyses unambiguously indicate that their electronic structures run the gamut from CC localized (group 13) to CN localized (group 16) via intermediate, more delocalized, systems. In particular, neither the stibenium ion nor any of the chalcogenium dications is a direct analogue of imidazol-2-ylidene as they all contain two lone pairs of electrons around the divalent main-group center, instead of the expected one. The reason behind the gradual change in the electronic structure of main-group analogues of imidazol-2-ylidene was traced to the total charge of the systems, which changes from anionic to dicationic when moving from left to right in the periodic table. Results from theoretical analyses of aromaticity show that all group 13−16 analogues of imidazol-2-ylidene display some degree of aromatic character. The heavier group 13 anions benefit the least from π-electron delocalization, whereas the cationic group 15 systems are on par with the parent carbon system and display only slightly less aromatic character than cyclopentadienide, a true 6π-electron aromatic species. The σ-donor and π-acceptor ability of the different main-group carbene analogues are also evaluated. ...
Publisher
ACS
ISSN Search the Publication Forum
0020-1669
Keywords
N-heterosykliset karbeenit elektronirakenne N-heterocyclic carbenes electronic structure
DOI
https://doi.org/10.1021/ic701350e
URI

http://urn.fi/URN:NBN:fi:jyu-201511183709

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/17432706

Metadata
Show full item record
Collections
  • Matemaattis-luonnontieteellinen tiedekunta [4955]

Related items

Showing items with similar title or keywords.

  • N-Heterocyclic Carbenes with Inorganic Backbones: Electronic Structures and Ligand Properties 

    Kausamo, Anna; Tuononen, Heikki; Krahulic, Kelly; Roesler, Roland (ACS, 2008)
    The electronic structures of known N-heterocyclic carbenes (NHCs) with boron, nitrogen, and phosphorus backbones are examined using quantum chemical methods and compared to the experimental results and to the computational ...
  • The influence of electron delocalization upon the stability and structure of potential N-heterocyclic carbene precursors with 1,3-diaryl-imidazolidine-4,5-dione skeletons 

    Hobbs, Matthew; Forster, Taryn; Borau-Garcia, Javier; Knapp, Chrissy; Tuononen, Heikki; Roesler, Roland (RSC, 2010)
    Targeting N-heterocyclic carbenes (NHCs) with increased π-acceptor character featuring N-fluorophenyl substituents, the molecular 2-chloro-1,3-bis(fluorophenyl)imidazolidine-4,5-diones (1a–c) were isolated from the ...
  • Extending the Series: Synthesis and Characterization of a Dicationic N-Heterocyclic Selenium Carbene Analogue 

    Dutton, Jason; Tuononen, Heikki; Jennings, Michael; Ragogna, Paul (ACS, 2006)
    The room-temperature reaction between the Dipp2DAB ligand, SnCl2, and SeCl4 results in the quantitative formation of a dicationic N-heterocyclic “carbenoid”. This represents the first example of a chalcogenium dication ...
  • A σ-Donor with a Planar Six-π-Electron B2N2C2 Framework: Anionic N-Heterocyclic Carbene or Heterocyclic Terphenyl Anion? 

    Forster, Taryn; Krahulic, Kelly; Tuononen, Heikki; McDonald, Robert; Parvez, Masood; Roesler, Roland (Wiley, 2006)
    NB! The anionic ligand 2 was synthesized through deprotonation of a planar, formally zwitterionic diazadiborine precursor, isolated as a lithium salt, and structurally characterized. According to experimental evidence and ...
  • Isolation of Free Phenylide-like Carbanions with N-Heterocyclic Carbene Frameworks 

    Krahulic, Kelly; Tuononen, Heikki; Parvez, Masood; Roesler, Roland (ACS, 2009)
    A series of 1,3-bis(2,6-diisopropylphenyl)-5-methyl-1,3-diaza-4,6-diborabenzenes with methyl, phenyl, and dimethylamino substituents on the ring boron atoms were prepared using the cyclocondensation reaction between ...
  • Browse materials
  • Browse materials
  • Articles
  • Conferences and seminars
  • Electronic books
  • Historical maps
  • Journals
  • Tunes and musical notes
  • Photographs
  • Presentations and posters
  • Publication series
  • Research reports
  • Research data
  • Study materials
  • Theses

Browse

All of JYXCollection listBy Issue DateAuthorsSubjectsPublished inDepartmentDiscipline

My Account

Login

Statistics

View Usage Statistics
  • How to publish in JYX?
  • Self-archiving
  • Publish Your Thesis Online
  • Publishing Your Dissertation
  • Publication services

Open Science at the JYU
 
Data Protection Description

Accessibility Statement

Unless otherwise specified, publicly available JYX metadata (excluding abstracts) may be freely reused under the CC0 waiver.
Open Science Centre