Cationic Complexes of 3a,6a-Diaza-1,4-diphosphapentalenes

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Abstract

The reactions of annulated 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes (DDPCl2) with 1 equiv. of trimethylsilyl triflate (TMSOTf) lead to replacement of one chlorine atom with the triflate group, thus giving cationic diazadiphosphapentalenes [ClDDP]+[TfO]−. In the presence of 2 equiv. of TMSOTf and 2 equiv. of 4‑dimethylaminopyridine (DMAP), the DDP dication stabilized by two DMAP molecules, [DDP(DMAP)2]2+[(CF3SO3)−]2, is formed. The DMAP molecules are located on one side of the DDP skeleton and lie in parallel planes. Free diazadiphosphapentalene was detected in solutions of [DDP(DMAP)2]2+[(CF3SO3)−]2 in CH2Cl2 by UV-Vis spectroscopy and CV. This implies that this compound disproportionates under these conditions; it is unstable in dilute solutions and decomposes to give [DMAP∙HOTf] in a quantitative yield. Crystallographic data for the obtained compounds: CCDC nos. 2182881–2182883.

About the authors

V. V. Sushev

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

Yu. S. Panova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

A. V. Khristolyubova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

N. V. Zolotareva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

M. D. Grishin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

E. V. Baranov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

G. K. Fukin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

A. N. Kornev

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

Author for correspondence.
Email: akornev@iomc.ras.ru
Россия, Нижний Новгород

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Copyright (c) 2023 В.В. Сущев, Ю.С. Панова, А.В. Христолюбова, Н.В. Золотарева, М.Д. Гришин, Е.В. Баранов, Г.К. Фукин, А.Н. Корнев