2,6-dimethylphenylimidotungsten(VI) tetrachloride | 150747-63-0

• 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: 2,6-dimethylphenylimidotungsten(VI) tetrachloride
• 英文别名: tetrachloro-(2,6-dimethylphenyl)iminotungsten
• CAS: 150747-63-0
• 化学式: C₈H₉Cl₄NW
• 分子量: 444.828
• InChiKey: QCRFWQWOZYGVLT-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  5.42
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-dimethylphenylimidotungsten(VI) tetrachloride 、 2,3-二羟基萘 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Ring size effects in phenol-phenolate tungsten (VI) chelates

  摘要：

  DOI：

  10.1021/ja00070a063
• 作为产物：
  描述：

  WCl4(N-2,6-C6H3Me2)(Et2O) 生成 2,6-dimethylphenylimidotungsten(VI) tetrachloride
  参考文献：
  名称：

  Synthesis of tungsten vinyl alkylidene complexes via the reactions of WCl2(NAr)(PX3)3 (X = R, OMe) precursors with 3,3-disubstituted cyclopropenes

  摘要：

  Several WCl2(NAr)(PX3)3 complexes were synthesized, including WCl2(N-2,6-C6H3Me2)(PEt2Ph)3 (1), WCl2(NPh)[P(OMe)3]3 (2), WCl2(N-2,6-C6H3Me2)[P(OMe)3]3 (3), and WCl2[N-2,6-C6H3(i-Pr)2][P(OMe)3]3 (4). NMR spectroscopic data for these complexes and a single-crystal X-ray diffraction study of 4 supported a meridional arrangement of the three PX3 ligands, all lying cis to the apical imido ligand. The lability of one PX3 ligand in complexes 1-4 was demonstrated by reactions with ethylene and phenyl- and diphenylacetylene to give the corresponding pi-acceptor (L) complex WCl2(L)(NAr)(PX3)2. In solution, some of the WCl2(L)(NAr)(PX3)2 complexes, especially those with P(OMe)3 ligands, were in equilibrium with WCl2(L)(NAr)(PX3) and free PX3; complete removal of 1 equiv of PX3 was achieved upon addition of CuCl. Complexes 1-4 and also WCl2(NPh)(PMePh2)3 reacted with 3,3-diphenylcyclopropene and 4,8-dioxaspiro[2.5]oct-1-ene (referred to subsequently as diphenyl- and ketalcyclopropene) to give a number of eta2-cyclopropene complexes and/or vinyl alkylidene complexes. Concentrated diethyl ether solutions of the reactants and use of the sterically smaller tungsten precursors enabled the clean formation of the eta2-cyclopropene complexes W(eta2-cyclopropene)Cl2(NAr)(PX3)2. Spectroscopic data and a single-crystal X-ray diffraction study of W(eta2-diphenylcyclopropene)Cl2(NPh)[P(OMe)3]2 indicated an octahedral geometry in which the two mutually trans PX3 ligands and the cyclopropene occupy equatorial positions cis to the apical imido ligand and the substituents of the cyclopropene lie syn to the imido ligand. The eta2-cyclopropene complexes were converted to the corresponding vinyl alkylidene complexes W(=CHCH=CR2)Cl2(NAr)(PX3)2 thermally, photochemically, and chemically (catalysis by HgCl2). For the reactions of the sterically more bulky tungsten precursors with cyclopropenes, direct isolation of the vinyl alkylidene complexes was possible. A crystal structure of an alkoxide derivative W(=CHCH=CPh2)[N-2,6-C6H3-(i-Pr)2][OCMe(CF3)2]2[P(OMe)3] confirmed the formation of a diphenylvinyl alkylidene ligand with an s-trans arrangement of the double bonds. In addition to an s-trans isomer, the ketalvinyl alkylidene ligand also formed two different s-cis isomers with one oxygen atom of the ketal ring chelating to tungsten. A crystal structure showed that, in one of these isomers, the ketal ring has been opened by a chloride ligand from tungsten, and a mechanism is proposed for this rearrangement.

  DOI：

  10.1021/ja00071a026

文献信息

• Supramolecular assemblies of tungsten complexes with unusual chelating groups
  作者：Timothy E. Baroni、Vladimir Kolesnichenko、Lawrence Seib、Joseph A. Heppert、Louise M. Liable-Sands、Glenn P.A. Yap、Arnold E. Rheingold

  DOI：10.1016/s0277-5387(97)00313-6

  日期：1998.3

  Metal complexes of ligands with η1-O coordinated carbonyl moieties are well-known throughout the inorganic literature. However, metal complexes containing authentic acid chloride ligands have not previously been isolated. The synthesis and characterization of compounds with the formula W(X)Cl3(OPh-2-COCl) (2) [X  O (2a), NC6H3-2,6-(CH3)2 (2b), and Ph2C2 (2c)] are reported. The crystal structures of 2a

  摘要在整个无机文献中，具有η1-O配位羰基的配体金属配合物是众所周知的。但是，以前没有分离出含有真正的酰氯配体的金属配合物。具有式W（X）Cl3（OPh-2-COCl）（2）[XO（2a），NC6H3-2,6-（CH3）2（2b）和Ph2C2（2c）的化合物的合成和表征）]报告。解析了2a和2c的晶体结构，显示了酰氯羰基部分与钨中心的相互作用。配合物2c采用在固态具有六倍对称空隙的通道结构。如所预期的，2a的配位酰氯容易与亲核试剂反应，生成酯WOCl3（OPh-2-COPrn）（3）和酰胺WOCl3（OPh-2-CONHBut）（4a）。相关的酰胺络合物WOCl3（OPh-2-CONH2）（4b），通过WOCl4与水杨酰胺的反应合成的α-烯烃显示出无限链结构，该结构由酰胺基团和相邻钨配合物的氧代配体之间的氢键支持。η1-O配位的硝基化合物W（X）Cl3（OPh-2-NO2）（5）[XO（5a），NC6H3-2
• Combinatorial Screening of an In Situ Generated Library of Tungsten Oxyhalide and Imido Complexes for Olefin Metathesis
  作者：Duane R. Romer、Victor J. Sussman、Ken Burdett、Yu Chen、Kami J. Miller

  DOI：10.1021/co500087b

  日期：2014.10.13

  A series of substituted tungsten(VI) halides with general formula WECl4 (E = O or −NR (imido)) were screened via a high throughput study to identify potential new olefin metathesis catalysts. The tungsten species were treated with a series of aluminum alkyl activators and modifier ligands to generate active catalyst species in situ. Ring-opening metathesis polymerization (ROMP) of cyclooctene was used

  一系列通式为WECl 4的取代卤化钨（VI）通过高通量研究筛选了（E = O或-NR（亚氨基）），以确定潜在的新型烯烃复分解催化剂。用一系列烷基铝活化剂和改性剂配体处理钨物质，以原位产生活性催化剂物质。环辛烯的开环易位聚合反应（ROMP）用作初步筛选，以识别潜在的易位催化剂，对活性催化剂进行二次筛选，以评估其对极性官能团的耐受性。高通量运动的几种组合产生了用于环辛烯的ROMP的活性复分解催化剂。然而，在本研究中检查的催化剂均未显示出任何证据表明，通过次级环辛烯/乙酸丁酯筛选的结果确定了显着的极性官能团耐受性。
• The role of two-component catalysts containing chelating bisaryloxide ligands in controlling the stereochemistry of the metathesis polymerization of norbornene
  作者：Denise L. Barnes、Nancy W. Eilerts、Joseph A. Heppert、Wayne H. Huang、Martha D. Morton

  DOI：10.1016/s0277-5387(00)80260-0

  日期：1994.4

  The ring-opening metathesis polymerization of norbornene and 5,5-dimethylnorbornene has been studied with a range of tungsten(VI) ring-opening metathesis polymerization procatalysts containing chelating diolate ligands, including catechols, 1,8-dihydroxynaphthalene, 1,1'-bi-2-naphthol, biphenanthrol and bis(2-hydroxyphenyl) methane. One class of these catalysts, W(=X)(OArO)Cl2(THF) (X = O or NArMe2) was produced via alcoholysis reactions between W(=X)Cl4 and the respective diol. Polymers of norbornene produced with these catalysts showed a reasonable correlation between ring size and cis-selectivity. This effect is most likely steric in origin. Analyses of the tacticity of poly-5,5-dimethylnorbornene showed a correlation between high cis-olefin content and syndiotacticity, even when produced with catalysts containing asymmetric chelating diolate ligands.
• JOHNSON, LYNDA K.;VIRGIL, SCOTT C.;GRUBBS, ROBERT H.;ZILLER, JOSEPH W., J. AMER. CHEM. SOC., 112,(1990) N3, C. 5384-5385
  作者：JOHNSON, LYNDA K.、VIRGIL, SCOTT C.、GRUBBS, ROBERT H.、ZILLER, JOSEPH W.

  DOI：——

  日期：——