Ca(II) and Yb(II) complexes featuring M(C≡C)4 structural motif: enforced proximity or genuine η2‐bonding?

Author:

Lyubov Dmitry M.1,Zakaria Hamza12,Nelyubina Yulia V.34,Aysin Rinat R.34,Bukalov Sergey S.34,Trifonov Alexander A.134ORCID

Affiliation:

1. G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences Russia 49 Tropinina str., GSP-445 603950 Nizhny Novgorod

2. N. I. Lobachevsky State University of Nizhny Novgorod Gagarina Avenue 23 603950 Nizhny Novgorod Russia

3. A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences Gagarina Avenue 23 603950 Nizhny Novgorod Russia

4. 28 Vavilova str. 119334 Moscow Russia

Abstract

AbstractBis(carbazolide) complexes M[3,6‐tBu2‐1,8‐(RC≡C)2Carb]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.

Funder

Russian Science Foundation

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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