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Neodymium monochloride and monoallyl complexes {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2NdR (R = Cl, CH2CH=CH2) with the tridentate amidinate ligand in the catalysis of ring-opening polymerization of cyclic esters
Russian Chemical Bulletin ( IF 1.7 ) Pub Date : 2020-06-01 , DOI: 10.1007/s11172-020-2876-6
A. O. Tolpygin , O. A. Linnikova , T. A. Kovylina , A. V. Cherkasov , G. K. Fukin , A. A. Trifonov

The reaction of tridentate amidine 2-[Ph2P(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (1) containing the side-chain donor group Ph2P=O with NdCl[N(SiMe3)2]2 (2) in a molar ratio of2:1 afforded the neodymium bis(amidinate) monochloride complex {2-[Ph2P(O)]-C6H4NC(But)N(2,6-Me2C6H3)}2NdCl (3). The neodymium bis(amidinate) monoallyl complex {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2Nd(C3H5) (5) was synthesized by the elimination reaction between the tris-allyl derivative Nd(C3H5)3-(C4H8O2)2 (4) and amidine 1 in a molar ratio of 1:2 and by the exchange reaction between equimolar amounts of complex 3 and allylmagnesium bromide (C3H5MgBr). Complex 5 exhibits high activity as an initiator for the ring-opening polymerization of rac-lactide and ε-caprolactone, providing the conversion of up to 500 equivalents of the rac-lactide and ε-caprolactone within 5 and 2 min, respectively. The resulting polylactide samples have high number-average molecular weights ((47.38–93.02) · 103) and low polydispersity indices (Mw/Mn = 1.18–1.47). The polycaprolactone samples are characterized by high number-average molecular weights ((114.34–237.46) · 103) and a somewhat broadened molecular weight distribution (Mw/Mn = 1.87–2.40).

中文翻译:

一氯化钕和单烯丙基配合物 {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2NdR (R = Cl, CH2CH=CH2) 与三齿脒配体在开环聚合反应中的催化作用环酯类

三齿脒 2-[Ph2P(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (1) 含有侧链供体基团 Ph2P=O 与 NdCl[N(SiMe3)2]2 ( 2) 以 2:1 的摩尔比得到双(脒) 一氯化钕络合物 {2-[Ph2P(O)]-C6H4NC(But)N(2,6-Me2C6H3)}2NdCl (3)。钕双(脒)单烯丙基配合物 {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2Nd(C3H5) (5) 是通过三烯丙基衍生物 Nd 之间的消除反应合成的(C3H5)3-(C4H8O2)2(4)和脒1以1:2的摩尔比通过等摩尔量的络合物3和烯丙基溴化镁(C3H5MgBr)之间的交换反应得到。配合物 5 作为外消旋丙交酯和 ε-己内酯开环聚合的引发剂表现出高活性,在 5 和 2 分钟内提供高达 500 当量的外消旋丙交酯和 ε-己内酯的转化率,分别。所得聚乳酸样品具有高数均分子量 ((47.38–93.02) · 103) 和低多分散指数 (Mw/Mn = 1.18–1.47)。聚己内酯样品的特征在于高数均分子量 ((114.34–237.46) · 103) 和稍微加宽的分子量分布 (Mw/Mn = 1.87–2.40)。
更新日期:2020-06-01
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