論文

査読有り
2015年8月

Theoretical Study on Internal Alkyne/Vinylidene Isomerization in Group 8 Transition-Metal Complexes

Organometallics
  • Miho Otsuka
  • ,
  • Noriko Tsuchida
  • ,
  • Yousuke Ikeda
  • ,
  • Natacha Lambert
  • ,
  • Rina Nakamura
  • ,
  • Yuichiro Mutoh
  • ,
  • Youichi Ishii
  • ,
  • Keiko Takano

34
16
開始ページ
3934
終了ページ
3943
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/om501280c
出版者・発行元
AMER CHEMICAL SOC

DFT calculations on the transformation reaction of the internal alkynes [CpM(PhC equivalent to CC6H4R-p)-(dppe)](+) (M = Fe, Os; R = OMe, CO2Et, Cl) to the corresponding vinylidenes were carried out. It was found that the isomerization of all complexes of group 8 elements studied in the present work, as well as the Ru complex that had already been reported in our previous study, proceeds via a direct 1,2-aryl shift. For the Fe complex, two types of direct 1,2-aryl shifts (paths 1 and 2), which depend on the orientation of the alkyne/vinylidene parts, were found, and the activation free energy of path 2 is smaller than that of path 1. As for the Os complex, path 1 and another direct 1,2-shift, path 3, were obtained, and path 3 has smaller activation free energy, which is the case for the Ru complex. Therefore, the isomerization reaction of internal alkynes to vinylidenes proceeds through path 2 for the Fe complexes and path 3 for the Ru and Os complexes. The 1,2-migration reactions via path 2 for the Fe complex and path 3 for the Os complex were found to be nudeophilic, which is based on an orbital interaction corresponding to an electron transfer from a carbon on the migrating group to the atom being migrated, as well as for the Ru complexes. To evaluate the stability of the alkyne and vinylidene complexes, orbital interaction energies between an organometallic complex part and an internal alkyne or a vinylidene moiety were calculated by natural bond orbital (NBO) analysis. It was revealed that the Os complex has the strongest interaction, followed by the Ru and Fe complexes. Namely, both the internal alkyne complexes and the vinylidene complexes are more stabilized in a heavier metal complex The activation free energy for migration of the aryl or phenyl group is actually the lowest for the Fe complex among the three metals. These findings contribute to the development of the synthetic strategy of vinylidenes from internal alkynes.

リンク情報
DOI
https://doi.org/10.1021/om501280c
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000360322500004&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/om501280c
  • ISSN : 0276-7333
  • eISSN : 1520-6041
  • Web of Science ID : WOS:000360322500004

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