Electrochemically induced phosphorus-methyl bond formation involving the complex [Co(Ph2PCH2P(Ph) 2PPPPP(Ph) 2CH2PPh2)]BF4

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The electrochemical properties of [Co(Ph2PCH2P(Ph)2PPPPP(Ph)2CH2PPh2)]BF4 complex have been studied by the method of cyclic voltammetry. The electrochemical methylation of this complex have been cunducted in the presence of iodomethane which has led to the formation of phosphonium salt—ethylene bis(methyldiphenylphosphonium) diiodide as final product. It was found, that this reaction proceeds with the breakage of the P–P bonds in polyphosphorus ligand and with the formation of new P–C bonds.

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作者简介

Airat Kuchkaev

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS; Kazan (Volga region) Federal University

编辑信件的主要联系方式.
Email: 95ka@bk.ru
ORCID iD: 0000-0002-2284-0081
俄罗斯联邦, Kazan; Kazan

Aidar Kuchkaev

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS; Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID iD: 0000-0001-5980-9865
俄罗斯联邦, Kazan; Kazan

A. Sukhov

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS; Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID iD: 0000-0001-8481-8544
俄罗斯联邦, Kazan; Kazan

A. Ivanov

Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID iD: 0000-0002-9511-0653
俄罗斯联邦, Kazan

Kh. Khayarov

Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID iD: 0000-0003-2913-5120
俄罗斯联邦, Kazan

A. Dobrynin

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS; Kazan National Research Technical University named after A.N. Tupolev – KAI

Email: 95ka@bk.ru
ORCID iD: 0000-0002-4912-3699
俄罗斯联邦, Kazan; Kazan

O. Sinyashin

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS

Email: 95ka@bk.ru
ORCID iD: 0000-0002-2241-9764
俄罗斯联邦, Kazan

D. Yakhvarov

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS; Kazan (Volga region) Federal University

Email: yakhvar@iopc.ru
ORCID iD: 0000-0002-3906-8841
俄罗斯联邦, Kazan; Kazan

参考

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2. Fig. 1. Products of activation and transformation of the white phosphorus molecule in the coordination sphere of cobalt subgroup complexes with diphosphine (PCP and PNP) ligands.

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3. Fig. 2. CVA curves for complex 1 (5 × 10–3 M) (curve (a)) and CH3I (5 × 10–3 M) (curve (b)) in DMF medium in the presence of Bu4NBF4 (0.1 M). Working electrode – SU, v = 100 mV/s.

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4. Fig. 3. CVA curves for the system containing complex 1 (5 × 10–3 M) in the presence of increasing amounts of CH3I (0–5 equiv.) in DMF medium in the presence of Bu4NBF4 (0.1 M). Working electrode – SU, v = 100 mV/s. The CVA curve for the system containing complex 1 without the addition of CH3I is shown in gray background.

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5. Fig. 4. (a) Preparative electroreduction of complex 1 in the presence of CH3I. (b) Molecular structure of the [Ph2P(CH3)CH2P(CH3)Ph2]2+ dication in the crystal. Thermal displacement ellipsoids are shown with 50% probability. Hydrogen atoms and iodide anions are not shown. Ph carbon atoms are not labeled.

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