Synthesis and Electrochemical Properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2022 Oct 17

PMID 36247980

Authors

Almaz A Zagidullin

Farida F Akhmatkhanova

Mikhail N Khrizanforov

Robert R Fayzullin

Tatiana P Gerasimova

Ilya A Bezkishko

Vasili A Miluykov

Affiliations

Soon will be listed here.

Abstract

A novel representative of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide containing a chloro substituent in the -position of the aryl groups was obtained with a high yield based on the reaction of tributyl(1,2,3-triarylcyclopropenyl)phosphonium bromide and sodium polyphosphides. Further reaction of sodium 3,4,5-tris(3-chlorophenyl)-1,2-diphosphacyclopentadienide with [FeCp(η-CHCH)][PF] complex gives a new 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene. The electrochemical properties of 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene were studied and compared to 3,4,5-tris(4-chlorophenyl)-1,2-diphosphaferrocene. It was found that the position of the chlorine atom on the aryl fragment has an influence on the reduction potential of 1,2-diphosphaferrocenes, while the oxidation potentials do not change.

Citing Articles

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Keglevich G Beilstein J Org Chem. 2023; 19:89-90.

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References

Petrov A, Zagidullin A, Bezkishko I, Khrizanforov M, Kholin K, Gerasimova T . Synthesis, structure, and electrochemical properties of 4,5-diaryl-1,2,3-triphosphaferrocenes and the first example of multi(phosphaferrocene). Dalton Trans. 2020; 49(47):17252-17262. DOI: 10.1039/d0dt03281f. View

SCHERER , Hilt , Wolmershauser . [{Cp]. Angew Chem Int Ed Engl. 2000; 39(8):1425-1427. DOI: 10.1002/(sici)1521-3773(20000417)39:8<1425::aid-anie1425>3.0.co;2-1. View

Virovets A, Peresypkina E, Scheer M . Structural Chemistry of Giant Metal Based Supramolecules. Chem Rev. 2021; 121(23):14485-14554. DOI: 10.1021/acs.chemrev.1c00503. View

Komatsu K, Kitagawa T . Cyclopropenylium cations, cyclopropenones, and heteroanalogues-recent advances. Chem Rev. 2003; 103(4):1371-427. DOI: 10.1021/cr010011q. View

Brake H, Peresypkina E, Heindl C, Virovets A, Kremer W, Scheer M . From nano-balls to nano-bowls. Chem Sci. 2019; 10(10):2940-2944. PMC: 6429618. DOI: 10.1039/c8sc05471a. View

Piesch M, Dielmann F, Reichl S, Scheer M . A General Pathway to Heterobimetallic Triple-Decker Complexes. Chemistry. 2019; 26(7):1518-1524. PMC: 7028134. DOI: 10.1002/chem.201905240. View

Li T, Gamer M, Scheer M, Konchenko S, Roesky P . P-P bond formation via reductive dimerization of [Cp*Fe(η5-P5)] by divalent samarocenes. Chem Commun (Camb). 2013; 49(22):2183-5. DOI: 10.1039/c3cc38841g. View

Lyons D, Crocker R, Blumel M, Nguyen T . Promotion of Organic Reactions by Non-Benzenoid Carbocyclic Aromatic Ions. Angew Chem Int Ed Engl. 2016; 56(6):1466-1484. DOI: 10.1002/anie.201605979. View

Bai J, Virovets A, Scheer M . Synthesis of inorganic fullerene-like molecules. Science. 2003; 300(5620):781-3. DOI: 10.1126/science.1081119. View

10.

Peresypkina E, Heindl C, Virovets A, Brake H, Madl E, Scheer M . Anionic Hosts for the Incorporation of Cationic Guests. Chemistry. 2017; 24(10):2503-2508. PMC: 5947592. DOI: 10.1002/chem.201705883. View

11.

Butovskiy M, Balazs G, Bodensteiner M, Peresypkina E, Virovets A, Sutter J . Ferrocene and pentaphosphaferrocene: a comparative study regarding redox chemistry. Angew Chem Int Ed Engl. 2013; 52(10):2972-6. DOI: 10.1002/anie.201209329. View

12.

Ogasawara M, Watanabe S, Nakajima K, Takahashi T . Enantioselective synthesis of planar-chiral phosphaferrocenes by molybdenum-catalyzed asymmetric interannular ring-closing metathesis. J Am Chem Soc. 2010; 132(7):2136-7. DOI: 10.1021/ja910348z. View

13.

Wolf R, Ehlers A, Khusniyarov M, Hartl F, de Bruin B, Long G . Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1). Chemistry. 2010; 16(48):14322-34. DOI: 10.1002/chem.201001913. View

14.

Wang L, Hollis T . Demonstration of a phosphazirconocene as a catalyst for the ring opening of epoxides with TMSCl. Org Lett. 2003; 5(14):2543-5. DOI: 10.1021/ol034816r. View

15.

Carmichael D, Goldet G, Klankermayer J, Ricard L, Seeboth N, Stankevic M . A comparison of phosphaferrocene and phospharuthenocene ligands in Rh+-catalysed enamide hydrogenation reactions: superior performance of the phospharuthenocene. Chemistry. 2007; 13(19):5492-502. DOI: 10.1002/chem.200601715. View

16.

Ranga P, Ahmad F, Singh G, Tyagi A, Vijaya Anand R . Recent advances in the organocatalytic applications of cyclopropene- and cyclopropenium-based small molecules. Org Biomol Chem. 2021; 19(44):9541-9564. DOI: 10.1039/d1ob01549d. View

17.

Fu G . Applications of planar-chiral heterocycles as ligands in asymmetric catalysis. Acc Chem Res. 2006; 39(11):853-60. DOI: 10.1021/ar068115g. View

18.

Reichl S, Madl E, Riedlberger F, Piesch M, Balazs G, Seidl M . Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus. Nat Commun. 2021; 12(1):5774. PMC: 8486752. DOI: 10.1038/s41467-021-26002-7. View

19.

Garrett C, Fu G . pi-Bound Phosphorus Heterocycles as Catalysts: Ring Opening of Epoxides with TMSCl in the Presence of a Phosphaferrocene. J Org Chem. 1997; 62(13):4534-4535. DOI: 10.1021/jo970419g. View

20.

Heinl C, Peresypkina E, Balazs G, Madl E, Virovets A, Scheer M . The Missing Parent Compound [(C H )Fe(η -P )]: Synthesis, Characterization, Coordination Behavior and Encapsulation. Chemistry. 2021; 27(27):7542-7548. PMC: 8252565. DOI: 10.1002/chem.202100203. View