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

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Resumo

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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Sobre autores

Airat Kuchkaev

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

Autor responsável pela correspondência
Email: 95ka@bk.ru
ORCID ID: 0000-0002-2284-0081
Rússia, 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
Rússia, 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
Rússia, Kazan; Kazan

A. Ivanov

Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID ID: 0000-0002-9511-0653
Rússia, Kazan

Kh. Khayarov

Kazan (Volga region) Federal University

Email: 95ka@bk.ru
ORCID ID: 0000-0003-2913-5120
Rússia, 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
Rússia, 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
Rússia, 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
Rússia, Kazan; Kazan

Bibliografia

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  6. Cecconi, F., Ghilardi, C.A., Midollini, S., and Orlandini A., A tetraphosphorus chain as part of a P 8 -containing ligand. Synthesis and properties of the.eta.4-phosphabutadiene cobalt complex [Co(Ph 2 PCH 2 P(Ph) 2 P- 4 P(Ph) 2 CH 2 PPh 2 )]BF 4 and of its carbonyl derivatives {[Co(Ph 2 PCH 2 P(Ph) 2 P 4 P(Ph) 2 CH 2 PPh 2 )][Cr(CO) 5 ] 2 }BF4 and {[Co(Ph 2 PCH 2 P(Ph) 2 P 4 P(Ph) 2 CH 2 PPh 2 )][W(CO) 5 ]}Y Y = BPh 4 , BF 4 ). X-ray crystal structure of [Co(Ph 2 PCH 2 P(Ph) 2 P 4 P(Ph) 2 CH 2 PPh 2 )]BF 4 , Inorg. Chem., 1986, vol. 25, p. 1766.
  7. Yakhvarov, D., Barbaro, P., Gonsalvi, L., Mañas Carpio, S., Midollini, S., Orlandini, A., Peruzzini, M., Sinyashin, O., and Zanobini, F., A snapshot of P4 tetrahedron opening: Rh- and Ir-mediated activation of white phosphorus, Angew. Chem. Int. Ed., 2006, vol. 45, p. 4182; Angew. Chem., 2006, vol. 118, p. 4288.
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  15. Бендерский, В.А., Кривенко, А.Г., Курмаз, В.А., Симбирцева, Г.В. Реакции n-алкильных радикалов на ртутном электроде. Электрохимия. 1988. Т. 24. С. 158,
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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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