Synthesis, structure, and electrochemical properties of 4, 5-diaryl-1, 2, 3-triphosphaferrocenes and the first example of multi(phosphaferrocene). Issue 47 (17th November 2020)

• Record Type: Journal Article
• Authors: Petrov, Andrey V.; Zagidullin, Almaz A.; Bezkishko, Ilya A.; Khrizanforov, Mikhail N.; Kholin, Kirill V.; Gerasimova, Tatiana P.; Ivshin, Kamil A.; Shekurov, Ruslan P.; Katsyuba, Sergey A.; Kataeva, Olga N.; Budnikova, Yulia H.; Miluykov, Vasili A.
• Is Part Of: Dalton transactions. Volume 49:Issue 47(2020)
• Page Start: 17252
• Page End: 17262
• Publication Date: 2020-11-17
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt03281f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Novel 1, 2, 3-triphosphaferrocenes have been extensively studied experimentally (NMR, UV-Vis, and X-ray) and quantum chemically. Abstract : The reaction between aryl substituted sodium 1, 2, 3-triphospholides or disodium bis(1, 2, 3-triphospholide) and [Fe(η 6 -(C6 H5 CH3 )Cp] + [PF6 ] − in boiling diglyme results in pure 1, 2, 3-triphosphaferrocenes 1–3 or bis(1, 2, 3-triphosphaferrocene) 4, respectively, in good yields. The structure of all obtained 1, 2, 3-triphosphaferrocenes 1–4 has been extensively studied experimentally (NMR, UV-Vis spectroscopy, and X-ray analysis for 1 and 4 ) and quantum chemically. The electrochemical properties of 1, 2, 3-triphosphaferrocenes 1–4 in the solid state were studied for the first time and a reversible one-electron oxidation ( E 1/2 = 0.52–0.92 V vs . Fc + /Fc) was demonstrated for 1, 3, and 4 . In the case of 1, 4-bis(5-phenyl-4-(1, 2, 3-triphospaferrocenyl))benzene 4, consecutive oxidation in the solid state is observed in contrast to other 1, 2, 3-triphosphaferrocenes 1–3 . According to the ESR data, the g -factor of the oxidized bis(1, 2, 3-triphosphaferrocene), 4 ( g = 2.12) is different from the g -factors of oxidized 1, 2, 3-triphosphaferrocenes 1–3 ( g = 2.01). This is the first example of multi(ferrocenyl) systems based on the phosphaferrocene motif, which in turn opens up a new fundamental platform for the preparation of compounds with stimuli-responsive properties.