| In the general conditions, the high activity of the transition metal hydride is due to some advantageous process of its reaction. In this thesis, some Ruthenium Hydrides were synthesized and applied to Transfer Hydrogenation for two purposes: one is that a project (200410436) from Jilin Company of China Petroleum is required to solve deep isomerization ofα-olefin (the Flory-Schulz distribution) from olefin oligomerization in industry for the balance ofα-olefin by the Metathesis, particularly 1-butene and high olefin (〉C18=); the other is the catalytic reduced ketone, which is the one of important transformation methods in organic synthesis, and its products are the significant chemicals or intermediates, the key question is to enhance the efficiency of the catalytic system. So it presents that the Ruthenium hydrides catalyze the hydrogenation transfer reactions-the olefin isomerization in intramolecular and the ketone reduction in intermolecular.The main contents of this thesis are as follows:(1) It is convenient and effective to synthesize transition metal hydrides by the reduction of the transition metal chloride and the ligand exchange. RuHCl (PPh3)3(s) (7), rather than RuHCl(CO)(PPh3)3, was rapidly and conveniently synthesized by another extremely simple route using RuCl2(PPh3)3 (1) and alcohol in the presence of a base, its yield comes up to 90%, ruthenium hydrides were synthesized: RuH(NO)(PPh3)3 (2), RuHCl(CO)(PPh3)3 (3), RuH(CH3CO2)(PPh3)3 (4), RuH2(CO) (PPh3)3 (5) and RuH2(PPh3)4 (6). Based on the RuHCI(PPh3)3(s), ruthenium hydrides RuH(PPh3)2(NHC-H) (10), RuHCI(N-P)2 (11), RuHCl(TPPTS)3 (8) and RuHCl(PPh3)2(en) (9) were respectively synthesized by ligands exchange with NHC and N-P, TPPTS and en.(2) In view of the insert-elimination process of the olefin isomerization, it was studied that ruthenium hydrides catalyzed the olefin isomerization, RuHCl(PPh3)3(s) was screened for the further investigation on the basis of the activity and the life-operating on isomerization of 1- hexene and 1-octadecene. 1-Hexene was converted into other two isomers of 19.29% 2-hexene and 78.25% 3-hexene on the condition of catalyst- 1.1×10-5 mol (in 1 mL toluene), temperature-120℃, time-30 mins, 1-hexene- 4 mL, which showed the deep isomerization of the olefin, and GC presented no byproducts except hexene isomers; the dynamic process was checked for 1-hexene isomerization by RuHCI(PPh3)3(s), the reaction rate constant was 10-3 min-1 at 25℃, its activity energies were Ea1=71.8 kJ/mol and Ea2=67.9 kJ/mol respectively. Moreover 1-octadecene isomerization by RuHCI(PPh3)3(s) was of the high activity, thermal stability and the solvent-free system; at 180℃the equilibrium conversion of 1-octadecene reached above 94.6% under the condition of the 1/200 (the catalyst/ the substrate) (tool).(3) New effective catalytic system was tried in situ for the ketone reduction, different substrates got the yields of 60%-99% under the condition of substrates/ RuHCI(PPh3)3(s)/ KOH /NH2(CH2)3OH=5000/1/1/1.In a word, the synthesis of RuHCl(PPh3)3(s) by reducing RuCl2(PPh3)3, RuHCI(PPh3)3(s) catalyzed the olefin isomerization and the ketone reduction, which are all related to hydrogenation transfer.
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