Investigation of organometallic complexes and their application in catalysis, biological activities and crystal engineering

Abstract

Preparation of Ru3(CO)8-pyridine-alcohol cluster and its use for selective catalytic transformation of primary to secondary amines.  Synthesis of tetranuclear Ru4(CO)8-substituted pyridine-methanol cluster and its use as a highly efficient electro-catalyst in water oxidation reaction.  Synthesis of new Ru3(CO)8-picolinic-acid cluster for catalytic oxidation of alcohols to carboxylic acids in basic water medium.  To prepare supra-molecular assemblies of triptycene – ferrocene and its derivatives and study their non-bonding interactions and packing features.  To synthesize and examine ferrocene-substituted bis(ethynyl)-anthracene/ anthraquinone compounds for biological activities. The thesis includes six chapters which begin with a general introduction (Chapter 1), followed by catalytic properties of the newly synthesized Ru3(CO)12 based clusters in the Chapters 2, 3 and 4. Furthermore, Chapter 5 includes ferrocene anthracene/anthraquinone based complexes which are examined for their anticancer biological property. Chapter 6 contains the report on co-crystals explored by the supra-molecular assembly of organometallic ferrocene and its derivatives with triptycene, followed by conclusions. Chapter 7 highlights conclusions and scope for future work. The introductory chapter (Chapter 1) of the thesis illustrates the brief literature of ruthenium-based catalyst, specific for N-alkylation and oxidation of alcohols to carboxylic acids, and water oxidation. We have included the background of the supramolecular chemistry of ferrocene and triptycene with different molecules. Furthermore, the background knowledge of ferrocene derivatives and anthracene/anthraquinone derivatives with their biological importance has also been discussedChapter 2 mainly focuses on ruthenium-based pyridine alcohol clusters and their application for mono N-alkylation catalytic reaction of primary amines using primary alcohols to form secondary amines. After chelation effect observations,[1,2] the preparation of ruthenium-substituted pyridine-alcohols have been carried out by reacting different pyridine alcohols, i.e. 2-(2-hydroxyethyl)pyridine (hep-H), 2-(3-hydroxypropyl)pyridine (hpp-H) and 2,6-bis(hydroxymethyl)pyridine (bhmp-H2) with Ru3(CO)12 in basic medium (Scheme 1). The prepared clusters 1–3 were confirmed by NMR, IR and authenticated by Single crystal x-ray diffraction (SCXRD) study.In Chapter 3, after the inspiration from ruthenium-substituted pyridinealcohol clusters, synthesis of the ruthenium-substituted pyridinecarboxylic acid complexes was carried out (Scheme 2) by adding picolinic acid to Ru3(CO)12 in toluene at 110 °C temperature for 4 h . The structure