WCl4(N-2,6-C6H3Me2)(Et2O)

• 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: WCl4(N-2,6-C6H3Me2)(Et2O)
• 英文别名: [W((2,6-dimethylphenyl)imido)Cl4(Et2O)]；Ethoxyethane;tetrachloro-(2,6-dimethylphenyl)iminotungsten；ethoxyethane;tetrachloro-(2,6-dimethylphenyl)iminotungsten
• 化学式: C₁₂H₁₉Cl₄NOW
• 分子量: 518.951
• InChiKey: AGGWJCTYCACMMI-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  6.47
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  WCl4(N-2,6-C6H3Me2)(Et2O) 在 THF 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 WCl4(N-2,6-C6H3Me2)(THF)
  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
• 作为产物：
  描述：

  2,6-二甲苯基异氰酸酯 、 tungsten oxytetrachloride 在 (C₂H₅)2O 作用下， 以 乙醚 、 甲苯 为溶剂， 以97.8%的产率得到WCl4(N-2,6-C6H3Me2)(Et2O)
  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

• Alkylidene and Metalacyclic Complexes of Tungsten that Contain a Chiral Biphenoxide Ligand. Synthesis, Asymmetric Ring-Closing Metathesis, and Mechanistic Investigations
  作者：W. C. Peter Tsang、Kai C. Hultzsch、John B. Alexander、Peter J. Bonitatebus,、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1021/ja0210603

  日期：2003.3.1

  most cases and high % ee in asymmetric reactions. Exploration of the reaction between 2a and a stoichiometric amount of one desymmetrization substrate allowed two intermediate tungstacyclobutane complexes to be observed, in addition to the final and quite stable tungstacyclobutane complex formed in a reaction between the ring-closed product and a tungsten methylene complex. Reactions involving 13C labeled

  包含外消旋或对映体纯 (S) 形式的 3,3'-二叔丁基-5,5',6,6'-四甲基-1,1'-联苯-2,2'-的两种配合物二醇 (Biphen2-) 配体，W(NAr)(CHCMe2Ph)(Biphen) (2a) 和 W(NAr')(CHCMe2Ph)(Biphen) (2b) (Ar = 2,6-i-Pr2C6H3；Ar' = 2 ,6-Me2C6H3)，并被证明是几种有代表性的闭环反应的可行催化剂，在大多数情况下以良好的产率得到产物，在不对称反应中得到高 ee 百分比。除了在闭环产物与亚甲基钨配合物的反应中形成最终且非常稳定的钨环丁烷配合物之外，对 2a 与化学计量量的一种去对称化底物之间的反应的探索还允许观察到两种中间钨环丁烷配合物。
• Alkylidene transfer from phosphoranes to tungsten(IV) imido complexes
  作者：Lynda K. Johnson、Marcus Frey、Tammara A. Ulibarri、Scott C. Virgil、Robert H. Grubbs、Joseph W. Ziller

  DOI：10.1021/ja00071a029

  日期：1993.9

  The reactions of WCl 2 (NPh)(PMePh 2 ) 3 with a number of triphenylphosphoranes were surveyed, and alkylidene transfer to give W(=CHR)Cl 2 (NPh)(PMePh 2 ) 2 was observed for variously substituted aryl ylides Ph 3 =CHAr', where Ar'=C 6 H 5 , C 6 H 4 -p-Me, C 6 H 4 -m-Me, C 6 H 4 -o-Me, C 6 H 4 -p-OEt, C 6 H 4 -o-OMe, C 6 H 4 -p-CF 3 , C 6 F 5 , o-Np, and m-Np, for the vinyl ylide Ph 3 P=CH-CH=CMe 2

  研究了 WCl 2 (NPh)(PMePh 2 ) 3 与许多三苯基膦的反应，并观察到亚烷基转移生成 W(=CHR)Cl 2 (NPh)(PMePh 2 ) 2 的各种取代芳基叶立德 Ph 3 =CHAR'，其中Ar'=C 6 H 5 、C 6 H 4 -p-Me、C 6 H 4 -m-Me、C 6 H 4 -o-Me、C 6 H 4 -p-OEt、C 6 H 4 -o-OMe、C 6 H 4 -p-CF 3 、C 6 F 5 、o-Np 和 m-Np，对于乙烯基叶立德 Ph 3 P=CH-CH=CMe 2 ，以及对于双(叶立德)Ph 3 P=CH-C 6 H 4 -C 6 H 4 -CH=PPh 3 。提出了转移反应的机制
• Synthesis of tungsten vinyl alkylidene complexes via the reactions of WCl2(NAr)(PX3)3 (X = R, OMe) precursors with 3,3-disubstituted cyclopropenes
  作者：Lynda K. Johnson、Robert H. Grubbs、Joseph W. Ziller

  DOI：10.1021/ja00071a026

  日期：1993.9

  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.