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  Diradical Character Enhancement by Spacing: N-Heterocyclic Carbene Analogues of Müller's Hydrocarbon

Rottschäfer, D., Busch, J., Neumann, B., Stammler, H.-G., van Gastel, M., Kishi, R., et al. (2018). Diradical Character Enhancement by Spacing: N-Heterocyclic Carbene Analogues of Müller's Hydrocarbon. Chemistry – A European Journal, 24(62), 16537-16542. doi:10.1002/chem.201804524.

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 Creators:
Rottschäfer, Dennis1, Author
Busch, Jasmin1, Author
Neumann, Beate1, Author
Stammler, Hans-Georg1, Author
van Gastel, Maurice2, Author              
Kishi, Ryohei3, Author
Nakano, Masayoshi3, 4, Author
Ghadwal, Rajendra S.1, Author
Affiliations:
1Anorganische Molekülchemie und Katalyse, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Bielefeld, Germany, ou_persistent22              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Osaka, Japan, ou_persistent22              
4Institute for Molecular Science, Myodaiji, Okazaki, Japan, ou_persistent22              

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Free keywords: carbenes; Chichibabin's hydrocarbon; Müller's hydrocarbon; open-shell; radicals
 Abstract: Two‐fold C−C cross‐coupling of N‐heterocyclic carbenes [NHCs; SIPr=C(NArCH2)2, 1; IPr=C(NArCH)2, 2; Me‐IPr=C(NArCMe)2, 3; Ar=2,6‐iPr2C6H3] with 4,4′′‐diiodo‐p‐terphenyl under Ni catalysis furnished [(SIPr)(C6H4)3(SIPr)](I)2 (4), [(IPr)(C6H4)3(IPr)](I)2 (5), and [(Me‐IPr)(C6H4)3(Me‐IPr)](I)2 (6). Two‐electron reduction of 4–6 with KC8 readily afforded NHC analogues of Müller's hydrocarbon (MH), [(SIPr)(C6H4)3(SIPr)] (7), [(IPr)(C6H4)3(IPr)] (8), and [(Me‐IPr)(C6H4)3(Me‐IPr)] (9), respectively, as highly colored crystalline solids. Quantum chemical calculations suggested that the singlet ground state for 7–9 possesses a vertical singlet–triplet energy gap ΔES‐T of −7.24 to −7.60 kcal mol−1, which is significantly lower compared to that of the NHC analogues of Thiele's (TH) and Chichibabin's (CH) (18–38 kcal mol−1) hydrocarbons. Importantly, the calculated diradical character (y) of 7–9 (y≈0.6) is considerably higher compared to that of the related TH and CH (y=0.1–0.4), suggesting the open‐shell singlet character of 7–9.

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Language(s): eng - English
 Dates: 2018-09-042018-09-062018-11-09
 Publication Status: Published online
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201804524
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 24 (62) Sequence Number: - Start / End Page: 16537 - 16542 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058