Exploring the Optimal Synthetic Pathways towards µ‐Carbido Diruthenium(IV) Bisphthalocyaninates

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 w...

Full description

Saved in:
Bibliographic Details
Published in:European journal of inorganic chemistry 2019-04, Vol.2019 (14), p.1923-1931
Main Authors: Kroitor, Andrey P., Martynov, Alexander G., Gorbunova, Yulia G., Tsivadze, Aslan Yu, Sorokin, Alexander B.
Format: Article
Language:English
Subjects:
Carbido complexes
Carbonyl complexes
Catalysis
Chemical Sciences
Chloroform
Dimerization
Dimers
Environment and Society
Environmental Sciences
Inorganic chemistry
Phthalocyanines
Refluxing
Ruthenium
Sandwich complexes
Substitutes
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 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 NMe4OH), which affords target complexes in high yield. 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. Series of substituted µ‐carbido diruthenium(IV) bisphthalocyaninates [Pc*Ru]2(µ‐C) (where Pc* = tert‐butyl, n‐butoxy‐ and crown‐substituted ligands) were synthesized either by direct metalation of phthalocyanines or via dimerization of [Pc*Ru](CO) by dichlorocarbene generated in situ from chloroform and basic reagents.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201900029