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Exploring the Optimal Synthetic Pathways towards µ‐Carbido Diruthenium(IV) Bisphthalocyaninates
Author(s) -
Kroitor Andrey P.,
Martynov Alexander G.,
Gorbunova Yulia G.,
Tsivadze Aslan Yu.,
Sorokin Alexander B.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900029
Subject(s) - chemistry , metalation , medicinal chemistry , reactivity (psychology) , monomer , tetra , yield (engineering) , porphyrin , dichlorocarbene , chloroform , stereochemistry , ruthenium , catalysis , photochemistry , organic chemistry , polymer , medicine , materials science , alternative medicine , pathology , metallurgy
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 Ru 3 (CO) 12 in refluxing o ‐dichlorobenzene where [Pc*Ru] 2 (µ‐C) are formed as by‐products 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 NMe 4 OH), which affords target complexes in high yield. Application of the appropriate base – NMe 4 OH was found to be crucial in the case of synthesis of crown‐substituted µ‐carbido dimers. Reaction of Ru 3 (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.