Exploring the Optimal Synthetic Pathways towards $\mathrmμ$-Carbido Diruthenium(IV) Bisphthalocyaninates

Kroitor, A.P.; Martynov, A.G.; Gorbunova, Y.G.; Tsivadze, A.Y.; Sorokin, A.B.

Авторы: Kroitor Andrey P., Martynov Alexander G., Gorbunova Yulia G., Tsivadze Aslan Yu, Sorokin Alexander B.
Журнал: European Journal of Inorganic Chemistry
Том: 2019
Номер: 14
Год издания: 2019
Издательство: John Wiley & Sons Ltd.
Местоположение издательства: United Kingdom
Первая страница: 1923
Последняя страница: 1931
DOI: 10.1002/ejic.201900029
Аннотация: Series of substituted µ‐carbido diruthenium(IV) bisphthalocyaninates [Pc*Ru]2(μ‐C), where Pc* ‐ tetra‐tert‐butyl, octa‐n‐butoxy‐, tetra‐15‐crown‐5‐ and hexa‐n‐butoxy‐mono‐(15‐crown‐5)‐substituted ligands were synthesized using two alternative approaches – (i) direct metalation of phthalocyanines with Ru3(CO)12 in refluxing o‐dichlorobenzene where [Pc*Ru]2(μ‐C) are formed as byproducts together with monomeric complexes [Pc*Ru](CO) and (ii) dimerization of [Pc*Ru](CO) by dichlorocarbene generated in situ from chloroform and bases (KOH or NMe4OH), which affords target complexes in high yields. Application of the appropriate base – NMe4OH was found to be crucial in the case of synthesis of crown‐substituted µ‐carbido‐dimers. Reaction of Ru3(CO)12 with the phthalocyanine bearing bulky mesityloxy‐groups yielded solely monomeric complex which could not be dimerized under any studied conditions. Therefore, the influence of nature of peripheral substituents in phthalocyanines on their reactivity in metalation and dimerization reactions was revealed.
Добавил в систему: Мартынов Александр Германович

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Exploring the Optimal Synthetic Pathways towards $\mathrmμ$-Carbido Diruthenium(IV) Bisphthalocyaninatesстатья

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