由双齿和三齿脒基配体支撑的钪和钇双（烷基）配合物。异戊二烯和1-庚烯聚合反应中的合成、结构及催化活性

Sc and Y bis(alkyl) complexes supported by bidentate and tridentate amidinate ligands. Synthesis, structure and catalytic activity in polymerization of isoprene and 1-heptene.

作者信息

Tolpygin Aleksei O, Sachkova Anastasia A, Mikhailychev Alexander D, Ob'edkov Anatoly M, Kovylina Tatyana A, Cherkasov Anton V, Fukin Georgy K, Trifonov Alexander A

机构信息

Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina str., GSP-445, 603950, Nizhny Novgorod, Russia.

Institute of Organoelement compounds of Russian Academy of Sciences, 28 Vavilova str., 119334, Moscow, Russia.

出版信息

Dalton Trans. 2022 May 17;51(19):7723-7731. doi: 10.1039/d2dt00866a.

DOI:10.1039/d2dt00866a

PMID:35522255

Abstract

A series of bis(alkyl) complexes {(Bu)C[N(2,6-MeCH)]}Ln(CHSiMe)(THF) (Ln = Y, = 1 (1); Ln = Sc, = 1 (2)), {2-[PhP(O)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (3), {2-[PhP(NPh)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (4) coordinated by bidentate (N,N) and tridentate (N,N,O; N,N,N) amidinate ligands are synthesized using an alkane elimination approach. Yttrium complex 1 demonstrated a half-life of ∼2.5 days at room temperature in benzene-D6 (CD) solution, whereas scandium complexes proved to be much more stable (25 d (2), 30 d (3) and 42 d (4)). Complexes 1-4 as a part of ternary catalytic systems 1-4/TB, HNB/AlR (AlR = AliBu, AliBuH; TB = [PhC][B(CF)], HNB = [PhNHMe][B(CF)]) demonstrated high catalytic activity in isoprene polymerization and enable 80%-100% conversion of 1000 equivalents of monomer into polymer at 25 °C within 3-180 min. The isolated polyisoprenes feature predominantly -1,4-regularity (69.2%-87.3%) and polydispersities / = 2.26-8.92. Moreover, the binary (2/TB) and ternary (1-4/TB/10 AliBu) systems initiate 1-heptene polymerization providing 40%-100% conversion of 500 equivalents of monomer in 24 h at 25 °C giving polymer samples with = 1.55-190.2 × 10 and / = 1.55-3.87.

摘要

通过烷烃消除法合成了一系列由双齿（N，N）和三齿（N，N，O；N，N，N）脒基配体配位的双（烷基）配合物{（Bu）C[N（2，6-MeCH）]}Ln（CHSiMe）（THF）（Ln = Y， = 1（1）；Ln = Sc， = 1（2）），{2-[PhP（O）]CHNC（Bu）N（2，6-MeCH）}Sc（CHSiMe）（3），{2-[PhP（NPh）]CHNC（Bu）N（2，6-MeCH）}Sc（CHSiMe）（4）。钇配合物1在室温下于苯-D6（CD）溶液中的半衰期约为2.5天，而钪配合物则稳定得多（25天（2），30天（3）和42天（4））。配合物1-4作为三元催化体系1-4/TB，HNB/AlR（AlR = AliBu，AliBuH；TB = [PhC][B（CF）]，HNB = [PhNHMe][B（CF）]）的一部分，在异戊二烯聚合中表现出高催化活性，能够在25°C下3至180分钟内将1000当量的单体80%-100%转化为聚合物。分离得到的聚异戊二烯主要具有-1,4-规整度（69.2%-87.3%），多分散性 /= 2.26-8.92。此外，二元体系（2/TB）和三元体系（1-4/TB/10 AliBu）引发1-庚烯聚合，在25°C下24小时内使500当量的单体转化率达到40%-100%，得到的聚合物样品 = 1.55-190.2×10， /= 1.55-3.87。