First examples of bispidine-ferrocene cyclophanes

First examples of bispidine-ferrocene cyclophanes Full article

Journal

Journal of Organometallic Chemistry
ISSN: 1872-8561 , E-ISSN: 0022-328X

Output data

Year: 2021, Volume: 949, Article number : 121945, Pages count : DOI: 10.1016/j.jorganchem.2021.121945

Authors

Medved'ko A.V. ¹ , Krut'ko D.P. ² , Gaisen S.V. ¹ , Churakov A.V. ³ , Minyaev M.E. ¹ , Moiseeva A.A. ² , Lemenovsky D.A. ² , Yu H. ⁴ , Vatsadze S.Z. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect, 47, Moscow 119991, Russian Federation.
2	Department of Chemistry; Lomonosov Moscow State University; Leninskie Gory 1-3 Moscow 119991 Russian Federation
3	N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky Prospect, 31, Moscow 119991, Russian Federation.
4	State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, PR China.

Two approaches for the syntheses of bispidine-ferrocene cyclophanes were reported. Both include the acylation of 1,5-dimethylbispidin-9-one (H2Bp) or its pendant amino-armed derivative by 1,1’-ferrocenoyl (Fc(CO)2) dichloride. The first approach allowed to isolate di-, tri- and pentameric cyclic oligomers of composition (BpFc(CO)2)n. The second one included the preliminary functionalization of H2Bp by N-protected glycine followed by deprotection and cyclization with Fc(COCl)2. The crystal structure of two new bispidine-ferrocene cyclophanes was established by single-crystal X-ray study. This study revealed the anti-conformation of amido-groups attached to the bispidine nitrogen atoms for both molecules. Various NMR techniques were applied to study the solution behavior of the macrocycles; the predominant anti-conformation in solution was also proved. The acyclic model compound Bp(FcCO)2 also showed only anti-conformer as revealed by VT-NMR and X-ray studies. Cyclic voltammetry study showed the difference in oxidation potentials of the Fc moiety within the row Bp(FcCO)2 – (BpFc(CO)2)2 – (BpFc(CO)2)3 with splitting of the oxidation curve in two later cases. The results obtained in this work will find an application in design and study of novel bispidine-ferrocene cyclophanes for the purposes of supramolecular sensing and catalysis.

Medved'ko A.V. , Krut'ko D.P. , Gaisen S.V. , Churakov A.V. , Minyaev M.E. , Moiseeva A.A. , Lemenovsky D.A. , Yu H. , Vatsadze S.Z.
First examples of bispidine-ferrocene cyclophanes
Journal of Organometallic Chemistry. 2021. V.949. 121945 . DOI: 10.1016/j.jorganchem.2021.121945 WOS Scopus OpenAlex

Web of science:	WOS:000703521400010
Scopus:	2-s2.0-85108422689
OpenAlex:	W3166599064

DB	Citing
OpenAlex	6
Scopus	5
Web of science	5