Synthesis of Novel Alkylcobaloxime Complexes and Study of Intermolecular Solid-state Reaction

Research Project

Project/Area Number	13640547
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Single-year Grants
Section	一般
Research Field	Organic chemistry
Research Institution	Nigata University of Phermacy and Applied Life Sciences
Principal Investigator	ARAI Yoshifusa Niigata University of Pharmacy and Applied Life Sciences, Faculty of Pharmacy, Research Assistant, 薬学部, 助手 (40202725)
Project Period (FY)	2001 – 2003
Project Status	Completed (Fiscal Year 2003)
Budget Amount *help	¥3,700,000 (Direct Cost: ¥3,700,000) Fiscal Year 2003: ¥400,000 (Direct Cost: ¥400,000) Fiscal Year 2002: ¥400,000 (Direct Cost: ¥400,000) Fiscal Year 2001: ¥2,900,000 (Direct Cost: ¥2,900,000)
Keywords	Solid-state / Cobaloxime / X-ray crystallography / Photoreaction / O_2-insertion / Cobalt / Cobalt-carbon bond / Alkyldioxicomplex / 固相反応 / 結晶格子 / 反応速度 / アルキルコバロキシム錯体
Research Abstract	The solid-state reactions of cobaloxime complexes, racemization and isomerization, were controlled by volume and shape of the cavity. Two different factors seems to control the reactive space in the crystal lattice, 1)a intermolecular interaction, for example the hydrogen-bond, and 2)a intramolecular effect. for example a bulky ligand. Novel γ-N-Phenylcarbamoylpropyl cobaloxime complexes were prepared. Irradiation of visible light on the crystals of these complexes caused decomposition to olefin, though olefin have not been observed in the case of γ-cyanopropyl complexes. X-ray crystallographical analysis of γ-N-phenylcarbamoylpropyl complex showed that the tightness of the cavity and the intermolecular hydrogen-bond between the carbamoyl group and hydroxyl group on the neighboring molecule limited motion of the reactive group in the crystal lattice. Further, β-allyloxyethyl cobaloxime complexes coordinated with diphenylglyoximes as bulky in-plane ligand were prepared. Irradiation of vis … More ible light on these complexes caused isomerization to a-substituted complexes and insertion of O_2 molecule into cobalt-carbon bond. In the solid-state, O_2-insertion reaction have scarcely reported, although it is typical in solution-state. O_2 molecule could enter the crystal by enlargement of the cavity. β-Phenylethyl, γ-phenylpropyl, β-pheoxyethyl, β-cyanoethyl, and β-methoxycarbonylethyl cobaloximes coordinated with diphenylglyoximes were also prepared. The reactivity of the photoreaction of these complexes varied with the axial base and with the substituents on the alkyl group. X-ray crystallographical analysis of these complexes revealed the fact that the increase of basicities of axial base distorts the plane of diphenylglyoximes to the direction of the axial base and neighboring molecules come closely into the expanded space around the reactive group. Then, the volume of cavity becomes smaller and the reactivity decreases. On the basis of these results, I expect to control the cavity and the reactivity of solid-state reaction and, to design new solid-state reactions. Less