Coordinative Reaction And Structural Characterization Of Ruthenium Complexes Supported By Phosphine?Sulfur And Carboxylato Ligands

Ruthenium compounds have attracted extensive research because of their wide applications in hydrogenation and desulfurization.In this thesis,a series of ruthenium compounds containing phosphine–sulfur and carboxylato ligands have been designed and synthesized.The novel ruthenium compounds were characterized by IR,NMR and X-ray crystallography pectrocopics spectroscopic.Organophosphorus compound?Ph₂PNHpy?has been prepared by the reaction of 2-amino pyridine with chlorodiphenyl phosphine,when PL1 reacted with Chalcogenide,the ligands Ph₂P?Q?NHpy?Q=O,S,Se?were accordingly obtained in excellent yield.Treatment of these ligands with [Ru?DMSO?4Cl₂],RuCl₂??⁶-p-cymene?]2 and other commun ruthenium?II?staring materials in refluxing tetrahydrofuran?THF?or toluene gave complexes [Ru?PPh₃?₂Cl₂??¹-N-Ph₂P?S?NHpy?]?1?,[Ru?DMSO?₂Cl₂??¹-N-Ph₂P?S?NHpy?]?2?,[Ru??⁶-p-cymene?Cl??²-N,N-Ph₂ P?S?Npy?]?3?,[Ru?THT?₂Cl₂??¹-N-Ph₂P?S?NHpy?]?4?,[Ru??⁶-benzene?-Cl₂??¹-N-Ph₂P?S?NHpy?]?5?,[Ru??⁶-p-cymene?Cl??²-N,N-Ph₂P?O?Npy?]?6?,[Ru??⁶-benzene?Cl₂??¹-N-Ph₂P?O?NHpy?]?7?,[Ru??⁶-p-cymene?Cl??²-N,N-Ph₂ P?Se?Npy?]?8?and [Ru??⁶-benzene?Cl₂??¹-N-Ph₂P?Se?NHpy?]?9?,respectively.The crystal structures of 3 and 5 have been determined by single-crystal X-ray diffraction,Complexes 3 and 5 have been applied in catalytic reduction of acetophenone to phenethyl alcohol.Reaction of [Ru?PPh₃?₃Cl₂] with the 2-methyl-acrylic acid 3-trimethoxysilane propyl ester in the presence of triethylamine?Et₃N?afforded the neutral 17 e ruthenium?III?-carboxylato complex [RuCl₂{?2-O,O-O₂CC=CH₂?CH3?}?PPh₃?₂]?10?as a result of the break of ester functional group.Interaction of [Ru?PPh₃?₃Cl₂] with 2-chlorobenzoic acid under similar reaction conditions gave the 17 e carboxylato ruthenium?III?complex [RuCl₂??2-O,O-O₂CC₆H₄-2-Cl??PPh₃?₂]?11?.Treatment of 2 with two equivalent n-Bu Li,followed by addition of SO₂ and Et₃ N resulted the cyclo-metallated 18 e ruthenium?II?complex [Et₃NH][RuCl?SO₂???2-C,O-C₆H₄-2-CO₂??PPh₃?₂]?12?.When [Et₄N]Clwas used instead of SO₂ and Et₃ N,the reaction also yielded the cyclo-metallated 18 e ruthenium?II?complex [Et₄N]2 [RuCl₂??2-C,O-C₆H₄-2-CO₂??PPh₃?₂]?13?.The four complexes were characterized by NMR,IR,MS and elemental analysis.Their structures were also characterized by single crystal X-ray diffraction.Molecular orbital calculations of complexes 10–13 are presented by the B3 LYP functional methods.