Synthesis of Group 4 Complexes That Contain the Tridentate Diamido/Donor Ligands [(ArylNCH2CH2)2O]2- and Zirconium Complexes That Contain [(ArylNCH2CH2)2S]2- and an Evaluation of Their Activity for the Polymerization of 1-Hexene
Synthesis of Group 4 Complexes That Contain the Tridentate Diamido/Donor Ligands [(ArylNCH2CH2)2O]2- and Zirconium Complexes That Contain [(ArylNCH2CH2)2S]2- and an Evaluation of Their Activity for the Polymerization of 1-Hexene
复制标题
含有三齿二酰氨基/供体配体 [(ArylNCH2CH2)2O]2- 的第 4 族配合物和含有 [(ArylNCH2CH2)2S]2- 的锆配合物的合成及其对 1-己烯聚合活性的评价
DOI：
10.1021/om980512a
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发表时间：
1998
期刊：
影响因子：
2.8
通讯作者：
R. Schrock
中科院分区：
文献类型：
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作者：
M. Aizenberg;Laura Turculet;W. M. Davis;F. Schattenmann;R. Schrock
在四氢呋喃中，(芳基=2，6-Me2C6H3(H2[1a]))，2，6-Et2C6H3(H2[1b])，2，6-i-Pr2C6H3(H2[1c])与(TsOCH2CH2)2O(TsOCH2CH2)2O(Tso=对甲苯磺酸盐)反应可以得到(ArylNHCH2CH2)2O(芳基=2，6-Me2C6H3(H2[1a])，2，6-Et2C6H3(H2[1b])，2，6-i-Pr2C6H3(H2[1c]))。合成了[1a，b]TiCl2，[1a，b]Time2，[1a]Ti(CH2Ph)2，[1a−c]M(NMe2)2(M=Zr或Hf)，[1a−c]MCl2，[1a−c]MR2(R=Me，Et，i-Bu)。[1a]Ti(CH2Ph)2的X-射线研究表明，其结构为扭曲的三方双金字塔(B型)，其中两个氨基氮和一个苯基配体占据赤道位置。对[1a]ZrMe2的X射线研究表明，它是一个扭曲的三角双金字塔，含有“轴向”氨基(A型)，而对[1c]HfEt2的X射线研究表明，它具有介于A型和B型之间的结构，即在顶端位置有一个烷基的扭曲方形金字塔。合成了含硫取代氧的类似化合物[(2，6-Me2C6H3NHCH2CH2)2S](H2[2a])，[(2，6-I-Pr2C6H3NHCH2CH2)2S](H2[2c])，[2a，c]Zr(NMe2)2，[2a，c]ZrCl2，[2a，...
Compounds of the type (ArylNHCH2CH2)2O (Aryl = 2,6-Me2C6H3 (H2[1a]), 2,6-Et2C6H3 (H2[1b]), 2,6-i-Pr2C6H3 (H2[1c])) can be prepared by treating (TsOCH2CH2)2O (TsO = tosylate) with the lithium anilides in THF. [1a,b]TiCl2, [1a,b]TiMe2, [1a]Ti(CH2Ph)2, [1a−c]M(NMe2)2 (M = Zr or Hf), [1a−c]MCl2, and [1a−c]MR2 (R = Me, Et, i-Bu) were prepared. An X-ray study of [1a]Ti(CH2Ph)2 revealed the structure to be a distorted trigonal bipyramid (type B) in which the two amido nitrogens and one benzyl ligand occupy equatorial positions. An X-ray study of [1a]ZrMe2 showed it to be a distorted trigonal bipyramid that contains “axial” amido groups (type A), while an X-ray study of [1c]HfEt2 revealed it to have a structure halfway between type A and type B, i.e., a distorted square pyramid with one alkyl in the apical position. Analogous compounds were also prepared that contain a sulfur donor instead of oxygen, i.e., [(2,6-Me2C6H3NHCH2CH2)2S] (H2[2a]), [(2,6-i-Pr2C6H3NHCH2CH2)2S] (H2[2c]), [2a,c]Zr(NMe2)2, [2a,c]ZrCl2, [2a,...