EPR spectroscopy study of the radical cation cluster  (η5-C5H5)(CO)5ReFePt(μ3-C=CHPh)(η2-Ph2P(CH2)2PPh2)

Chemistry, Vol 12, No 4 (2019)

EPR spectroscopy study of the radical cation cluster (η5-C5H5)(CO)5ReFePt(μ3-C=CHPh)(η2-Ph2P(CH2)2PPh2)

Nikolay Gennadievich Maksimov, Victor Vasilievich Verpikin, Dmitry Valerievich Zimonin, Galina Veniaminivna Burmakina, Oleg Sergeevich Chudin, Anatoly Iosifovich Rubaylo

Abstract

The chemical oxidation of the cluster CpReFePt(µ₃-C=CHPh)(CO)₅(dppe) (Cp = η⁵-C₅H₅, dppe = η²-Ph₂P(CH₂)₂PPh₂) resulted in a radical cation [CpReFePt(µ₃-C=CHPh)(CO)₅(dppe)]^+• that is sufficiently stable only at low temperature. An electronic structure of the radical cation was studied by EPR and following parameters were obtained by comparison of the experimental and a model spectrum: g_x= 2.070 g_y= 2.0295 g_z= 1.997; A_x(P³¹) = 17 A_y(P³¹) = 49 A_z(P³¹) = 35 (Gs);A_x(Pt¹⁹⁵) = 62 A_y(Pt¹⁹⁵) = 45 A_z(Pt¹⁹⁵) = 105 (Gs). An unpaired electron is seen to be mainly concentrated on the iron atom (85-90 %) and partially on the platinum atom (10-15%).

Further transformation of the radical cation led to the formation of the binuclear complex Cp(CO)₂RePt(μ=C=CHPh)(dppe) and the Fe-carbonyl fragment.