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Ca(II) and Yb(II) complexes featuring M(C≡C)4 structural motif: enforced proximity or genuine η2 -bonding?
Dmitry M Lyubov1, Hamza Zakaria1,2, Yulia V Nelyubina3,4
1G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Russia, 49 Tropinina str., GSP-445, 603950, Nizhny Novgorod.
Abstract:
Bis(carbazolide) complexes M[3,6-tBu2 -1,8-(RC≡C)2 Carb]2 (THF)n (R=SiMe3 , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe3 )2 ]2 (THF)2 with two molar equivalents of carbazoles. The complexes feature M(η2 -C≡C)4 structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η2 -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution. According to QTAIM analysis there are 4 bond critical points (3;-1) between the metal atom and each of the triple bonds, which are connected by a strongly curved, almost T-shaped bond pathway.
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