Reactions Of Pyridine-containing Alcohol Compounds With Triruthenium Dodecacarbonyl

Pyridine and its derivatives are of great important nitrogen heterocyclic ligands in the field of organometallic chemistry. For example the pyridine ligands play a key role in the development of organometallic chemistry. The N atom has a strong ability of coordination with transition metals because of their unshared pair electrons, and some of their complexes have wide applications in the organic chemistry.In this paper, reactions of substituted pyridine-containing alcohol compounds with Ru3(CO)12 were studied and seven kinds of new pyridine-alkoxide complexes were obtained. Six of the pyridine-alkoxide complexes were characterized by X-ray diffraction and their structures were discussed. In addition, we studied the the reactivity of pyridine-alkoxide complexes [PyCH2CH(Ph)O]2Ru3(CO)8 (6). The main results are listed as follows:(1) In this thesis, the different functional groups pyridine-containing alcohol compounds PyCH2CH(Ar)OH [Ar= Ph (1),4-MePh (2),4-ClPh (3)], PyCH2COPh (4) and PyCH2C(CH3)2OH (5) were designed and synthesized. Reactions of these substituted pyridine-containing alcohol compounds with Ru3(CO)i2 gave the corresponding seven pyridine-alkoxide complexes [PyCH2CH(Ph)O]2Ru3(CO)8 (6, 7)、[PyCH=C(Ph)O][PyCH=C(Ph))Ru(CO)2 (8)、[PyCH=C(4-MePh)O]2Ru3(CO)8 (9). [PyCH2CH(4-ClPh)O]2Ru3(CO)8 (10)、[PyCH=C(Ph)O]2Ru3(CO)8 (11) and [PyCH2C(CH3)2O]2Ru3(CO)8 (12). The results showed that 6、7、9、10、11and 12 were trinuclear ruthenium complexes. The structures of these complexes were similar, but complexes 6 and 7 were homogeneous crystals. Each of them contained two molecules ligands in which each of the O atoms of pyridine-containing alcohol compounds coordinated with two Ru atoms by the way of the oxygen-bridge respectively, but the third Ru atom was not involved which still maintaining the primary structure of Ru3(CO)12. The complex 8 was mononuclear biscyclometalated product which containing two different ligands. The pyridine-containing alcohol ligand coordinated with Ru atom to form six-membered ring, while vinylpyridine ligand coordinated with Ru atom to form five-membered ring via sp2C-H bond activation of the vinyl group.(2) The reactivity of complex 6 was studied. It reacted with cyclopentadiene or indene to give dinuclear metal carbonyl complexe [(η5-C5H5)Ru(CO)]2(μ-CO)2 or [(η5-C9H7)Ru(CO)]2(μ-CO)2. The results showed that the stability of complex 6 was poor than [(η5-C5H5)Ru(CO)]2(μ-CO)2 and [(η5-C9H7)Ru(CO)]2(μ-CO)2, so the reactivity of cyclopentadiene and indene with Ru3(CO)12 were higher than that of the pyridine-containing alcohol.