2,6-吡啶二亚胺基锰(Ⅲ)配合物的合成、晶体结构及催化性能

由三齿含氮配体2,6-二1-(2,6-二甲基苯基亚胺)乙基]吡啶(L1)、2,6-二1-(2,6-二乙基苯基亚胺)乙基]吡啶(L2)和2,6-二1-(2,4,6-三甲基苯基亚胺)乙基]吡啶(L3)分别与MnCl2·4H2O在乙腈中反应,合成了3个新的具有较大空间位阻的2,6-吡啶二亚胺基氯化锰配合物L1Mn(Ⅱ)...

Syntheses, Crystal Structures and Catalytic Performance of 2,6-Bis(imino)pyridyl Manganese Complexes

Reactions of equimolar rations of MnCl2?4H2O and the tridentate ligands 2,6-bis1-(2,6-dimethylphenylimino)ethyl]pyridine (L1), 2,6-bis1-(2,6-diethy phenylimino)ethyl]pyridine (L2), and 2,6-bis1-(2,6-dimethylphenylimino)ethyl]pyridine(L3) in acetonitrile afford the five-coordinated complexes L1Mn(II)Cl2?CH3CN(Mn1), L2Mn(II)Cl2?CH3CN(Mn2) and L3Mn(II)Cl2?CH3CN(Mn3), respectively. All complexes were characterized using elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystallographic studies on complexes Mn1–Mn3 reveal three complexes to be pentacoordinate with geometries that can be best described as distorted trigonal bipyramidal. Mn1 crystallizes in the monoclinic system, space group P21/n, with a = 1.3304(3) nm, b = 1.4864(3) nm, c = 1.4423(3) nm; β = 108.41(3)?, V = 2.7063(9) nm3, Z = 4, F(000) = 1116 , R1 = 0.0465. Mn2 belongs to monoclinic system with space group P21/c, with a = 1.2919(1) nm, b = 1.5283(1) nm, c = 1.6362(1) nm; β = 99.27(1)?, V = 3.1883(3) nm3, Z = 4, F(000) = 1244, R1 = 0.0599. Mn3 belongs to monoclinic system with space group P21/n, with a = 1.4542(3) nm, b = 1.5083(3) (1) nm, c = 1.4646(3) nm; β = 112.56(3)?, V = 2.9667(10) nm3, Z = 4, F(000) = 1180, R1 = 0.0627. Complexes Mn1–Mn3 exhibit lower catalytic activities for ethylene polymerization after activation with cocatalysts of Ph3C]+B(C6F5)4]-.