Syntheses And Characterizations Of RuCl₂(diphosphine)(diamine) Complexes And Application In Catalytic Hydrogenation Of Carbonyl Compounds

In this thesis, a series of RuCl2(diphosphine)(diamine) complexes such as [RuCl2(BDPX)(Ln)] ( L1 = NH2CH2CH2NH2; L2 = NH2(CH2)3NH2; L3 = NH2(CH2)4NH2; L4 = (S,S)-NH2CH(Ph)CH(Ph)NH2 ), [RuCl2(BISBI)(Ln)] and [RuCl2(PPh3)2(L2)] have been prepared and determined by 31P, 1H-NMR, IR spectroscopic and elemental analyses. Single-crystal X-ray structural investigations show [RuCl2(BDPX)(L1)] belongs to monoclinic system, P21/c space group with a = 1.8780(3) nm, b = 1.0722(2) nm, c = 1.7461(3) nm, β = 113.980(3)°, Z = 4; [RuCl2(BDPX)(L2)] to orthorhombic system, Pnma space group with a = 2.0419(3) nm, b = 1.7600(2) nm, c = 1.0062(1) nm, Z = 4; [RuCl2(BISBI)(L4)] to triclinic system, P-1 pace group with a = 1.0965(2) nm, b = 1.4026(3) nm, c = 1.6019(3) nm, α = 95.38(3)°, β = 97.95(3)°, γ = 110.67(3)°, Z = 2, and [RuCl2(PPh3)2(L2)] to monoclinic system, P21/c space group with a = 1.6977(2) nm, b = 1.0323(1) nm, c = 2.1087(3) nm, β = 107.843(3)°, Z = 4. With the exception of [RuCl2(BDPX)(L1)] and [RuCl2(BISBI)(L1)], all of the other ruthenium complexes are highly catalytic activity in the hydrogenation of acetophenone. The detail results of asymmetric hydrogenation of acetophenone catalyzed by the complex RuCl2(BISBI)(L4) are reported and the enantioselectivities for the formation of the (R)-1-phenylethanol were about 80% with quantitative conversion under mild conditions. The influences of different diphosphines and diamines have been also investigated. When using complex RuCl2(diphosphine)(L4) to hydrogenate asymmetrically the carbonyl group of acetophenone, changing the diphosphine would not affect the stereoselectivity under the experimental conditions. The selective hydrogenation of these complexes for benzylaceton has been investigated. Most of these complexes have been shown very good activity and excellent selectivity for the hydrogenation of C=O double bond under mild conditions. The hydrogenation of the dinuclear ruthenium complex [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] for ???-unsaturated aldehydes such as cinnamaldehyde also have shown that the resemble mechanism of RuCl2(diphosphine)(diamine) would work when introducing a ruthenium-equivalent amount of ethylenediamine.