The Synthesis, Structure And Properties Of Rutheium Organometallic Complexes With Sulfur Donor Ligands

In recent years there has been an increased interest in ruthenium complexes with sulfur donor ligands for their importance in the field of biological and industrial catalysis process. So we synthesized a series of novel and potential catalytic activity ruthenium complexes containing bidentate or tridentate thiolate ligands and detected their crystal structures. Moreover, reactivity along with spectroscopic and electrochemical properties has also been investigated in detail.Eleven mononuclear ruthenium compounds (1-11) sulfur-donor coordinate environment have been synthesized in this thesis. Then we have summarized the synthesis course and the mechanism for every reaction. The crystal structures of complexes have been determined by single-crystal X-ray diffraction. The ruthenium atom in each of the above complexes adopts a pseudo-octahedral geometry and the 1,1'-dithiolate ligands bind to ruthenium with bite S-Ru-S angles. With the aim of identifying reduction properties of low valence Ru(â…¡) center, the kinetic electronic absorption spectrum of reaction between complex 4 with strong oxidant (NH₃)₂Ce(NO₃)₆ was investigated. Electrochemical properties suggest that the ruthenium (â…¢) state in these complexes is well stabilized by the combination of of-donor phosphine and electron-rich sulfur ligandsFive novel and potential catalytic activity ruthenium compounds (12-16) containing poly(mercaptoimidazolyl)borate ligands were synthesized and characterized with elemental analysis, IR, NMR and X-ray crystallography. Crystal structure analysis of (12,13 and 15) confirmed that poly(mercaptoimidazolyl)borate ligand can provide a bidentate or tridentate facial coordination mode to form an overall distorted octahedral geometry. Coordination behavior of ligand depends on the properties of coligands. We have shown that poly(mercaptoimidazolyl)borate ligand is a very powerful ligand for ruthenium moieties through remarkably robust B-H…Ru agnostic interaction. Density Functional Theory (DFT) method calculations of the optimized structure, atomic charge distributions and vibrational frequencies for two compounds (12 and 13) were studied and compared with their corresponding experimental results.Treatment of [FcP(S)(u-S)]2 (Ferrocenyl Lawesson's Reagent) with different ruthenium materials in THF afforded three new complexes (17·CH₂Cl₂,18 and 19·CH₂Cl₂·³/₄C₆H₁₄). These compounds have been characterized by the infrared, UV-Vis, NMR spectroscopies and X-ray crystallography. Three compounds in CH₂Cl₂ solution can emit weak fluorescent due to poor quantum yields. Cyclic voltammogram of three heterobimetallic trinuclear compounds were semblable with other compounds containing ferrocenyldithiophosphonic ligand. Moreover, a novel ruthenium phosphorodithioate complex (20) containing M-S-S bond was synthesized and characterized firstly by X ray diffraction.Reaction of MoO₂(S₂CNMe₂)₂ with RuCl₃·xH2_O in acetone at reflux afforded a dinuclear ruthenium compound (21·2CH₃COCH₃) which was characterized by X-ray diffraction to show ruthenium-dithiocarbamate species as cation and hexamolybdate as counter anion. The [Ru₂(S₂CNMe₂)₃(μ₃-S₂CNMe₂)₂]⁺ cation may be considered as a combination of [Ru(S₂CNMe₂)₃] with a cis-[Ru(S₂CNMe₂)₂]⁺ species, and the Lindqvist anion [Mo₆O₁₉]^2- is located on an inversion center of two cations. Spectroscopic properties along with the electrochemistry of compound 21-2CH3COCH3 are reported. Furthermore, a mononuclear ruthenium complex (22) with arene ligands has been synthesized and structurally characterized.At the end of thesis, we report the synthesis and crystal structure of a Cp*Ir halfsandwich complex (23) containing azido and bis(diphenylthiophosphoryl)amide ligands.