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化合物3-{6-[(1R,2R,4S)-2-羟基-1,3,3-三甲基二环[2.2.1]庚烷-2-基]-吡啶-2-基}-1,1-′(R)-联萘-2,2′-酚(1)与特戊酰氯反应,得到单个羟基封端的化合物3-{6-[(1R,2R,4S)-2-羟基-1,3,3-三甲基二环[2.2.1]庚烷-2-基]-吡啶-2-基}-2′-特戊酰基-1,1′-(R)-联萘-2,2′-酚(2)。化合物2与MoO2(acac)2进行配位得到金属配合物3-{6-[(1R,2R,4S)-2-羟基-1,3,3-三甲基二环[2.2.1]庚烷-2-基]-吡啶-2-基}-2′-特戊酰基-1,1′-(R)-联萘-2,2′-酚合钼(酰)[Mo(Ⅵ)-2],通过核磁共振氢谱、红外光谱和质谱测试技术对其结构进行了表征,用X射线单晶衍射测定了化合物的晶体结构。结果表明,化合物晶体属单斜晶系,空间群为P21,晶胞参数a=1.179 34(10)nm,b=2.304 5(2)nm,c=1.518 88(13)nm,α=90,°β=112.84°,γ=90°,V=3.804 2(6)nm3,Z=4,μ=0.392 mm-1,Dc=1.298 Mg/m3,F(000)=1 544,R1=0.077 5,wR2=0.193 4,GOF=1.122。在配合物中,钼原子处于六配位的八面体配位环境,配位原子分别来自1个分子水中的O原子、配体分子中1个酚羟基的O,吡啶环中的O,醇羟基中的O形成ONO三齿配合物。配合物Mo(Ⅵ)-2在萘乙烯的不对称环氧化反应中,得到中等活性和较低的对映选择性。
Compound 3- {6 - [(1R, 2R, 4S) -2-hydroxy- 1, 3,3-trimethylbicyclo [2.2.1] heptan-2- yl] -pyridin-2-yl} - (1) is reacted with pivaloyl chloride to give a single hydroxy-terminated compound 3- {6 - [(1R, 2R, 4S) -2-hydroxy -1,3,3-trimethylbicyclo [2.2.1] heptan-2-yl] -pyridin-2-yl} -2’-pivaloyl- 1,1 ’- (R) -2,2’-phenol (2). Compound 2 is coordinated with MoO2 (acac) 2 to obtain the metal complex 3- {6 - [(1R, 2R, 4S) -2- hydroxy-1, 3,3-trimethylbicyclo [2.2.1] 2-yl] -pyridin-2-yl} -2’-pivaloyl- 1,1 ’- (R) 2]. The structure was characterized by 1H-NMR, FT-IR and MS-MS. The crystal structure of the compound was characterized by X-ray single crystal diffraction. The results show that the crystal of the compound belongs to the monoclinic system with a space group of P21. The unit cell parameters are a = 1.179 34 (10) nm, b = 2.304 5 (2) nm, c = 1.518 88 = Β = 112.84 °, γ = 90 °, V = 3.804 2 (6) nm3, Z = 4, μ = 0.392 mm-1, Dc = 1.298 Mg / , wR2 = 0.193 4, GOF = 1.122. In the complex, the molybdenum atom is in the hexacoordination octahedral coordination environment, and the coordination atoms come from O atoms in one molecule of water, O in the molecule of the phenolic group in the ligand molecule, O in the pyridine ring, and the alcoholic hydroxyl group O in the formation of ONO tridentate complexes. The complex Mo (Ⅵ) -2 in naphthalene asymmetric epoxidation, to obtain a moderate activity and lower enantioselectivity.