Vanadium(III) and -(IV) Complexes with O,N-Chelating Aminophenolate Ligands: Synthesis, Characterization and Activity in Ethene/Propene Copolymerization
Vanadium(III) and -(IV) Complexes with O,N-Chelating Aminophenolate Ligands: Synthesis, Characterization and Activity in Ethene/Propene Copolymerization
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DOI：
10.1002/1099-0682(20011)2001:1
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发表时间：
2001
影响因子：
2.3
通讯作者：
H. Hagen;J. Boersma;M. Lutz;A. Spek;G. Koten
中科院分区：
文献类型：
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作者：
H. Hagen;J. Boersma;M. Lutz;A. Spek;G. Koten
单阴离子的、潜在的二齿或三齿氨基酚盐（[OC 6 H 3（CH 2 NMe 2）-2-R-4）]-，R = H（a）、Me（B）、tBu（c）、Cl（d）、N=NPh（e）、MeO（f）和[OC 6 H 2（CH 2 NMe 2）2- 2，6-Me-4]-（g））已用于合成定义明确的用于α-烯烃聚合的钒基催化剂。[Cp 2 V]与g的母体酚反应导致钒（II）核的氧化，得到钒（III）（三）酚盐[V（OC 6 H2（CH 2NMe 2）2- 2，6-Me-4）3]（1）。[VCl_3（THF）_3]与苯酚钠反应，由于NaCl的掺入，不能得到钒（III）氨基苯酚盐。然而，使用相应的甲硅烷基醚Me 3SiOC 6 H3（CH 2NMe 2）-2-Me-4（2）导致形成氯钒（双）酚盐[VCl（OC 6 H3（CH 2NMe 2）-2-Me-4）2]（3）。尝试将3氧化成相应的二氯钒（IV）（双）苯酚盐没有成功。未观察到与CuCl、AgCl和PbCl 2的反应。与CuCl 2反应得到深蓝色化合物4，初步确定为VIII/CuII双核物种。在室温下在苯中或在回流温度下在甲苯中用SOCl 2处理钒（IV）氧代（双）酚盐5a-5 f导致形成深蓝色化合物6a-6 f，其化学计量表明过量的氯化物。只有当5a和5d在-70 °C下与SOCl 2反应时，才能得到所需的二氯钒（双）酚盐[VCl 2（OC 6 H4（CH 2NMe 2）-2-Cl-4）2]（7a）和[VCl 2（OC 6 H3（CH 2NMe 2）-2-Cl-4）2]（7 d）。1和3的X-射线晶体结构测定表明，这两种化合物具有三角双锥几何结构，两个氨基酚配体以类似的方式以双齿2-O，N方式结合到钒中心。测试化合物1、3、6和7的乙烯/丙烯共聚。
Monoanionic, potentially bi- or terdentate aminophenolates, ([OC6H3(CH2NMe2)-2-R-4)]-, R = H (a), Me (b), tBu (c), Cl (d), N=NPh (e), MeO (f) and [OC6H2(CH2NMe2)2-2,6-Me-4]- (g)), have been used in the synthesis of well-defined vanadium-based catalysts for the polymerization of -olefins. The reaction of [Cp2V] with the parent phenol of g resulted in oxidation of the vanadium(II) nucleus to obtain the vanadium(III) (tris)phenolate [V(OC6H2(CH2NMe2)2-2,6-Me-4)3] (1). Vanadium(III) aminophenolates could not be obtained by reaction of [VCl3(THF)3] with the sodium phenolates because of incorporation of NaCl. However, use of the corresponding silyl ether Me3SiOC6H3(CH2NMe2)-2-Me-4 (2) resulted in the formation of the chlorovanadium (bis)phenolate [VCl(OC6H3(CH2NMe2)-2-Me-4)2] (3). Attempts to oxidize 3 to the corresponding dichlorovanadium(IV) (bis)phenolate were not successful. No reaction was observed with CuCl, AgCl and PbCl2. A dark blue compound 4 was obtained with CuCl2, which was tentatively assigned as a VIII/CuII dinuclear species. Treatment of the vanadium(IV) oxo (bis)phenolates 5a-5f with SOCl2 in benzene at room temperature or in toluene at reflux temperature resulted in the formation of dark blue compounds 6a-6f, whose stoichiometries indicated excess chloride. Only when 5a and 5d were reacted with SOCl2 at -70 °C could the desired dichlorovanadium (bis)phenolates [VCl2(OC6H4(CH2NMe2)-2)2] (7a) and [VCl2(OC6H3(CH2NMe2)-2-Cl-4)2] (7d) be obtained. X-ray crystal structure determination of 1 and 3 showed that both compounds have a trigonal bipyramidal geometry with two aminophenolate ligands bound in a bidentate 2-O,N fashion to the vanadium center in similar ways. The compounds 1, 3, 6 and 7 were tested for ethene/propene copolymerization.