Synthesis And Properties Of Novel Iron,Cobalt And Nickel Complexes Supported By Sulfur-Containing Ligands

The development of transition metal hydrides has been nearly 100 years,many literatures summarized their synthesis and properties.Transition metal complexes are powerful tools for the activation of small molecule compounds.Synthetic metal catalysts are a key strategy for the development of new atomic and environmentally friendly catalytic processes.Metal complexes containing metal-sulfur bonds are abundant in living systems and play key roles in biologically relevant processes.Therefore,they are unusual and widely used in hydrogenation,hydrogen transfer,hydrosilylation,hydroformylation,carbonylation,Heck reaction,allyl alkylation,Grignard cross-coupling,polymerization,conjugate addition and oxidation addition.Due to the strong ? donor/? acceptor character and special steric hindrance,chlorosilylenes can be used to synthesize novel metal complexes as ligands.Sulfur-containing ligands are a preferred class of ligands that can be combined with a variety of metals to form metal complexes of various natures.Our group has done a lot of work and reports on the preparation and properties of metal complexes supported by[S,P]ligands.Based on the previous research work,The main research content of this paper is to synthesize novel metal complexes by using[S,P]and[SPS]ligands to react with iron,cobalt and nickel complexes,and explored the coordination properties of chlorosilylene.The specific research work of this paper is as follows:1.Two novel Fe-H complexes 4 and 5 were synthesized through the replacement of PMe3 by chlorosilylene.The two complexes were fully characterized by IR and NMR.Furthermore,there were two isomers 4a and 4b,5a and 5b in the solution of 4 and 5,respectively.2.The stable di-valent nickel chloride 6 was synthesized by the reaction of[S,P]bidentate ligand with NiCl2(PMe3)2.Two vinyl nickel complexes 7 and 8 were synthesized by reacting nickel hydride with two kinds of alkynes.The[S,P]-Ni-H complex was synthesized by reaction of[S,P]bidentate ligands with Ni(PMe3)4.3.Hydrothiolation of phenyl allene was carried out by using Ni(PMe3)4 as catalyst.The optimal condition of the reaction was explored.The reaction system had high selectivity in mild conditions.Under the optimal condition,we carried out the substrate expansion and realized the addition reactions of three kinds of phenyl allenes with three three kinds of thiophenols.We obtained products with three different configurations,of which 2a,3a,6a,7a can be determined to be in the Z configuration.However,aliphatic allene or aliphatic thiophenol was unsuitable for this catalytic system.4.The[SPS]tridentate ligand L2 was disgened and synthesized.The trivalent hydrido cobalt complex 9 was obatained by the reactions of the L2 with CoMe(PMe3)4 or CoCI(PMe3)3.Complex 9 was also characterized by IR and NMR analysis,and its structure was further confirmed by x-ray diffraction analysis.