W(CH-t-Bu)(N-2,6-diisopropylphenyl)(trifluoro-tert-butoxide)2 | 107440-83-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: W(CH-t-Bu)(N-2,6-diisopropylphenyl)(trifluoro-tert-butoxide)2
• 英文别名: [W(neopentylidene)(N(2,6-diisopropylphenyl))(O(trifluoro-tert-butyl))2]；(2,6-iPr2C6H3)N(tungsten)(OCMe2CF3)2(CHtBu)；[t-BuCH=W(N-2,6-(i-Pr)2C6H3)(OCMe2CF3)2]；t-Bu-CH=W(N(2,6-i-Pr2C6H3))(OCMe2CF3)2
• CAS: 107440-83-5
• 化学式: C₂₅H₃₉F₆NO₂W
• 分子量: 683.431
• InChiKey: HMFPDMVRKLKIJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  35.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  30.82
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  W(CH-t-Bu)(N-2,6-diisopropylphenyl)(trifluoro-tert-butoxide)2 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  钨（VI）金属环丁烷配合物的制备和反应活性。方形金字塔与三角双锥

  摘要：

  DOI：

  10.1021/om00159a024

文献信息

• Synthesis, structures and catalytic properties of germanium-containing tungsten alkylidene complex Me3Ge-CHW(NAr)(OR)2 and metallacycle [CH(GeMe3)CH(GeMe3)CH2]W(NAr)(OR)2
  作者：Leonid N. Bochkarev、Yulia E. Begantsova、Andrey L. Bochkarev、Natalia E. Stolyarova、Irina K. Grigorieva、Irina P. Malysheva、Galina V. Basova、Elena O. Platonova、Georgii K. Fukin、Evgenii V. Baranov、Yurii A. Kurskii、Gleb A. Abakumov

  DOI：10.1016/j.jorganchem.2006.08.029

  日期：2006.12

  isolated from the same reaction when twofold excess of Me3GeCHCH2 was used. The both compounds 1 and 2 were structurally characterized. They were found to have low activity in metathesis of 1-hexene and high activity in ROMP of cyclooctene and norbornene.

  钨Me 3 Ge-CHW（NAr）（OCMe 2 CF 3）2（1）（Ar = 2,6-Pr2iC6H3）的亚烷基络合物是通过Me 3 GeCHCH 2与已知的亚烷基化合物Bu t –CHMo反应制得的（NAr）（OCMe 2 CF 3）2的摩尔比为1：1。当两倍过量的Me 3 GeCHCH过量时，从同一反应中分离出金属环[CH（GeMe 3）CH（GeMe 3）CH 2 ] W（NAr）（OCMe 2 CF 3）2（2）使用了2。化合物1和2都在结构上进行了表征。发现它们在1-己烯的复分解中活性低，而在环辛烯和降冰片烯的ROMP中活性高。
• Effect of the nature of carbene fragments in the tungsten complexes PhMe2E-CH=W(NAr)(OR′)2 and Me3E-CH=W(NAr)(OR′)2 (E = C, Si) on their catalytic properties in olefin metathesis reactions
  作者：A. L. Bochkarev、Yu. E. Begantsova、E. O. Platonova、G. V. Basova、I. K. Grigor’eva、N. E. Stolyarova、I. P. Malysheva、G. K. Fukin、E. V. Baranov、Yu. A. Kurskii、L. N. Bochkarev、G. A. Abakumov

  DOI：10.1007/s11172-008-0253-y

  日期：2008.9

  Catalytic properties of the silicon-containing carbene complexes of tungsten Me3Si-CH=W(NAr)(OR′)2(1) and PhMe2Si-CH=W(NAr)(OR′)2 (2) and their hydrocarbon analogs Me3C-CH=W(NAr)(OR′)2 (3) and PhMe2C-CH=W(NAr)(OR′)2 (4) (Ar = 2,6-Pri 2C6H3, R′ = CMe2CF3) were studied in homometathesis of hex-1-ene, metathesis polycondensation of deca-1,9-diene, and ring opening metathesis polymerization of cyclooctene. The nature of the carbene fragment in the tungsten catalysts substantially affects their catalytic activity. Silicon-containing catalysts 1 and 2 were found to be 3−5 times less active than their hydrocarbon analogs 3 and 4. Metathesis polymerization of cyclooctene in the bulk with initiators 1–4 completed within a few minutes to form a block. Stereoregularity of the formed polyoctenamers depends to a considerable extent on the nature of the carbene fragments in the starting initiators. Initiators 1–2 lead to polyoctenamers mainly containing the cis-units, whereas the use of complexes 3 and 4 affords polyoctenamers mainly containing the trans-units. The structures of novel compound 2 and known complexes 1, 3, and 4 were determined by X-ray diffraction analysis.

  研究了Me3Si-CH=W(NAr)(OR′)2(1)和PhMe2Si-CH=W(NAr)(OR′)2(2)的含硅碳化钨配合物及其烃类似物Me3C-CH=W(NAr)(OR′)2(3)和PhMe2C-CH=W(NAr)(OR′)2(4)（Ar = 2、6-Pri 2C6H3, R′ = CMe2CF3）在己-1-烯的均相缩聚、癸-1,9-二烯的偏聚以及环辛烯的开环偏聚中进行了研究。钨催化剂中碳烯片段的性质对其催化活性有很大影响。研究发现，含硅催化剂 1 和 2 的活性比其碳氢化合物类似物 3 和 4 低 3-5 倍。用引发剂 1-4 对大块环辛烯进行 Metathesis 聚合反应在几分钟内完成，形成一个嵌段。所形成的聚辛烯酰胺的立体规整性在很大程度上取决于起始引发剂中碳烯片段的性质。引发剂 1-2 生成的聚八烯酰胺主要含有顺式单体，而使用复合物 3 和 4 生成的聚八烯酰胺主要含有反式单体。通过 X 射线衍射分析确定了新型化合物 2 和已知复合物 1、3 和 4 的结构。
• Carbene complexes of molybdenum and tungsten Et3E-CH=M(NAr)(OR)2 (M = Mo, W; E = Si, Ge) and π-complex of molybdenum (RO)2(ArN)Mo(CH2=CH-GeEt3). Synthesis and catalytic properties
  作者：Yu. P. Barinova、A. L. Bochkarev、Yu. E. Begantsova、L. N. Bochkarev、Yu. A. Kurskii、G. K. Fukin、A. V. Cherkasov、G. A. Abakumov

  DOI：10.1134/s1070363210100129

  日期：2010.10

  heteroelement-containing alkylidene imide complexes with molybdenum and tungsten Et3SiCH=Mo(NAr)(OR)2 (I), Et3 ECH=W(NAr)(OR)2 (E = Si (II), Ge (III); Ar = 2,6-i-Pr2C6H3; R=CMe2 CF3) and π-complex (RO)2(ArN)Mo(CH2=CH-GeEt3) (IV) were synthesized by the reaction of Alkyl-CH=M(NAr) (OR)2 (M=Mo, W; Alkyl = t-Bu, PhMe2C) with organosilicon and organogermanium vinyl reagents Et3ECH=CH2 (E = Si, Ge). The

  含杂元素的亚钼酰亚胺与钼和钨的络合物Et 3 SiCH = Mo（NAr）（OR）2（I），Et 3 ECH = W（NAr）（OR）2（E = Si（II），Ge（III）;合成Ar = 2,6- i -Pr 2 C 6 H 3 ; R = CMe 2 CF 3）和π络合物（RO）2（ArN）Mo（CH 2 = CH-GeEt 3）（IV）通过烷基-CH = M（NAr）（OR）2（M = Mo，W;烷基= t -Bu，PhMe 2C）用有机硅和有机锗乙烯基试剂Et 3 ECH = CH 2（E = Si，Ge）。化合物I–III的结构通过X射线衍射（XRD）确定。配合物I–IV是环烯烃复分解聚合的活性引发剂。
• Reaction of neopentylidene complexes of the type M(CH-t-Bu)(N-2,6-C6H3-i-Pr2)(OR)2 (M = W, Mo) with methyl acrylate and N,N-dimethylacrylamide to give metallacyclobutane complexes
  作者：Jerald Feldman、John S. Murdzek、William M. Davis、Richard R. Schrock

  DOI：10.1021/om00111a025

  日期：1989.9
• Feldman, Jerald; Davis, William M.; Schrock, Richard R., Organometallics, 1989, vol. 8, # 9, p. 2266 - 2268
  作者：Feldman, Jerald、Davis, William M.、Schrock, Richard R.

  DOI：——

  日期：——