Postsynthetic Modification of Half-Sandwich Ruthenium Complexes by Mechanochemical Synthesis

Abstract

A mild and environmentally friendly method to synthesize half-sandwich ruthenium complexes through the Wittig reaction between an aldehyde-tagged half-sandwich ruthenium complex and phosphorus ylide mechanochemically is reported herein. The mechanochemical synthesis of valuable half-sandwich ruthenium complexes resulted in a fast reaction, good yield with simple workup, and the avoidance of harsh reaction conditions and organic solvents. The synthesized half-sandwich ruthenium complexes exhibited high catalytic activity for transfer hydrogenation of ketones using 2-propanol as the hydrogen source and solvent. Density functional theory was carried out to propose a mechanism for the transfer hydrogenation process. The modeling suggests the importance of the labile p-cymene ligand in modulating the reactivity of the catalyst.

Mechanochemical synthesis of half‐sandwich iridium/rhodium complexes with 8‐hydroxyquinoline derivatives ligands

“…At this point, the formyl group in complex 1a afforded further chemical transformation to diverse functional half‐sandwich metal complexes. [ 58–62 ]…”

“…At this point, the formyl group in complex 1a afforded further chemical transformation to diverse functional half-sandwich metal complexes. [58][59][60][61][62] The molecular structures of complex 1b in the solid state were determined by single-crystal X-ray diffraction…”

Chemistry on the Complex: Derivatization of TiO4N2‐Based Complexes and Application to Multi‐Step Synthesis

“…Additionally, post-synthetic modification of organometallic complexes is a very attractive way to elaborate the next generations of metal complex catalysts. [23] Altogether, this non-exhaustive overview demonstrates that the chemistry on the complex is inextricably linked with the development of contemporary coordination chemistry. Titanium(IV) complexes belong to a major class of compounds that are intensively used in various fields of modern chemical science.…”

In vitro and in vivo antitumor activity of novel half-sandwich ruthenium complexes containing quinoline derivative ligands

“…34,35 In addition, quinoline derivatives have been widely used as metal complexes of ligands in biomedicine and as antitumor agents. [36][37][38][39][40] From the antitumor aspect, the high antitumor activity of the coordination complex of the 8-hydroxyquinoline ligand has become a promising candidate for platinum anticancer drugs. In previous work, Glazer et al prepared a series of ruthenium complexes containing hydroxyquinoline and bis-dimethyl-phenanthroline which verified the structure-activity relationship after the substitution of different sites.…”