Applications Of Tribenzylphosphine Derivatives In Molecular Gyroscope

Molecular machine in microcosmic world has been attacting the chemists for a long time. Molecular gyroscope, as a special one of molecular machines, has drawn extensive attention of the scientists to the design and synthesis of it, among whom, Garcia-Garibay's group and Gladysz's group have gained groundbreaking results in the research of gyroscope, and the type of P-M-P (M=Pt, Pd, Fe, Re and Rh) gyroscope developed by Gladysz's group inspired us particularly.After the research of the work of Gladysz's group, it is found that the gyroscope-like molecular using triphenylphosphine can not rotate freely in the crystalline state. Meanwhile, tribenzylphosphine (PBz3) with the great potential stemming from its excellent nucleophilicity and peculiar steric properties has received our great attention. Because of these reasons above, we introduce tribenzylphosphine ligand into the synthesis of gyroscope-like molecules, in hope of getting a gyroscope-like molecule that can rotate freely in the crystalline state.It was proved that the metal rotator trans-PdCl2{P[CH2C6H3-(o-O(CH2)3CH3) (m-CH3)]3}2 (2-12) could rotate freely in the crystalline state in theory after analysing the crystal structure of 2-12. With these results in hand, tribenzylphosphine ligands P[CH2(m-C6H4)O(CH2)4CH=CH2]3 (2-4) and dibenzylphosphine ligands PPh[CH2 (m-C6H4)O(CH2)4CH=CH2]2 (2-8) were designed and synthesized, and the complexes of trans-PdCl2{P[CH2(m-C6H4)(CH2)4CH=CH2]3}2 (2-5) and trans-PdCl2{PPh[CH2(m-C6H4)(CH2)4CH=CH2]2}2 (2-9) were obtained via the reactions between these ligands and palladium salt. Alkene metathesis of 2-5 and 2-9 using Grubst's catalyst produced metathesis products, hydrogenations of the metathesis products yielded three gyroscope-like molecules (2-7) and 2-11 (a, b)). Though the product of trans-2-1 could be separated, its structure could not be determined by NMR (1H, 13C and 31P). The products (2-11) of dibenzylphosphine ligands also could be obtained conveniently. The meta substitution of diphosphine ligands give both intraligand and interligand metathesis products.In summary, this dissertation has studied the possibilities using tribenzylphosphine derivatives in the research of gyroscope-like molecules, and synthetized the crystal molecular with shapes of molecular gyroscopes, which comes to be attemptation and foundation for future work.