trans-MoCl₄(Et₂O)₂ | 30411-56-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-MoCl₄(Et₂O)₂
• 英文别名: trans-(Et2O)2MoCl4；ethoxyethane;tetrachloromolybdenum
• CAS: 30411-56-4
• 化学式: C₈H₂₀Cl₄MoO₂
• 分子量: 385.998
• InChiKey: FWNHNOOFDTXSDJ-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  4.84
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-MoCl₄(Et₂O)₂ 以 neat (no solvent, solid phase) 为溶剂， 以99%的产率得到四氯化钼
  参考文献：
  名称：

  四氯双(二乙醚)钼(IV)制备钼配位化合物的改进

  摘要：

  在二乙醚中用金属锡还原 MoCl5 可以快速方便地进入 [MoCl4(OEt2)2] 这种化合物可以很容易地以高产率转化为各种其他有用的合成子。固态中醚的损失提供了一种新的反应形式的 MoCl4。用 THF、PMe3 或 LiOtBu 处理以高分离产率提供 [MoCl4(THF)2]、[MoCl4(PMe3)3] 或 [Mo(OtBu)4]。在 THF 中用金属锡处理得到 [MoCl3(THF)3] 所有这些反应都可以在简单的实验条件下进行，并且相对于先前报道的相同化合物的合成具有显着的改进。

  DOI：

  10.1002/1099-0682(200109)2001:10<2699::aid-ejic2699>3.0.co;2-s
• 作为产物：
  描述：

  乙醚 、 五氯化钼 生成 trans-MoCl₄(Et₂O)₂
  参考文献：
  名称：

  重新审视“MoCl3(dme)”：改进的合成、表征以及 X 射线和电子结构

  摘要：

  “MoCl 3 (dme)”（dme = 1,2-二甲氧基乙烷）是中价钼化学的重要前体，特别是对于 Mo 2 X 6类型的三重 Mo-Mo 键合化合物（X = 大体积阴离子配体）。然而，50 多年来，它的确切结构特性一直是模糊的。为了寻求方便的大规模合成，我们发现溶解在 dme中的反式MoCl 4 (Et 2 O) 2可以用二甲基苯基硅烷 Me 2 PhSiH彻底还原，以提供卡其色 Mo 2 Cl 6 (dme) 2约 90% 的产率。如果以小规模进行还原，可以获得适用于 X 射线晶体学的单晶。确定了两种不同的晶体形态，每种都属于P 2 1 / n空间群，但晶胞常数略有不同。每种形式的精制结构是一个共享边缘的双八面体，具有整体C i对称性和 2.8 Å 数量级的金属-金属分离。根据 Gouy 方法和 SQUID 磁力测定法确定，散装材料是抗磁性的。密度泛函理论计算表明 σ 2 π 2 δ*

  DOI：

  10.1021/acs.inorgchem.1c01398

文献信息

• Reactivity of the <i>ansa</i>-Bridged Metallocene Dichlorides [X(η⁵-C₅H₄)₂]MCl₂ (X = SiMe₂, CMe₂; M = Mo, W) toward Metallophosphide Anions [PPh₂M‘(CO)<i>_x</i>]^- (M‘ = Cr, Mo, W, <i>x</i> = 5; M‘ = Fe, <i>x</i> = 4). Formation of Heterobimetallic Complexes by Nucleophilic Substitution on a Cyclopentadienyl Ligand or on the Metal M
  作者：Virginie Comte、Olivier Blacque、Marek M. Kubicki、Claude Moïse

  DOI：10.1021/om970630i

  日期：1997.12.1

  Two kinds of ansa derivatives, [SiMe2(η5-C5H4)2]MCl2 and [CMe2(η5-C5H4)2]MCl2 (M = Mo, W), are reacted with metallophosphide anions [PPh2M‘(CO)x]- (M‘ = Cr, Mo, W, x = 5; M‘ = Fe, x = 4). The silicon-bridged derivatives give the bimetallic systems [SiMe2(η5-C5H4)(η5-C5H3PPh2M‘(CO)x)]M(H)(Cl), which result from a regioselective substitution at the 3-position on the cyclopentadienyl ligand. In contrast

  两种柄型衍生物，[森达2（η 5 -C 5 H ^ 4）2 ]的MC1 2和[CME 2（η 5 -C 5 H ^ 4）2 ]的MC1 2（M =钼，钨），与反应金属磷化物阴离子[PPh 2 M'（CO）x ] -（M'= Cr，Mo，W，x = 5； M'= Fe，x = 4）。的硅桥联衍生物得到的双金属系统[森达2（η 5 -C 5 H ^ 4）（η 5 -C 5 H ^3 PPh 2 M'（CO）x）] M（H）（Cl），这是由于在环戊二烯基配体的3位上进行了区域选择性取代。与此相反，与CME 2 -bridged化合物，发生取代反应在金属中心，给μ-膦双金属络合物[CME 2（η 5 -C 5 H ^ 4）2 ] M（Cl）的（μ-PPH 2） M'（CO）x。双金属配合物[CME的固态结构2（η 5 -C 5 H ^ 4）2 ] W（氯）（μ-PPH 2）的Fe（CO）4（7d）被报道。
• Molybdenum and Tungsten Complexes That Contain the Diamidoamine Ligands [(C₆F₅NCH₂CH₂)₂NMe]²^-, [(3,4,5-C₆H₂F₃NCH₂CH₂)₂NMe]²^-, and [(3-CF₃C₆H₄NCH₂CH₂)₂NMe]²^-
  作者：Frank V. Cochran、Adam S. Hock、Richard R. Schrock

  DOI：10.1021/om030638u

  日期：2004.2.1

  led to the formation of [C6F5NMe]MoMe2 (3), [C6F5NMe]Mo(CH2CMe3)Cl (4b), [C6F5NMe]W(CH2CMe3)Cl (5), [3,4,5-F3C6H2NMe]Mo(CH2CMe3)Cl (8), [3,4,5-F3C6H2NMe]Mo(CH2CMe3)(CCMe3) (9), [3,4,5-F3C6H2NMe]Mo(CH2SiMe3)2 (10), [3,4,5-F3C6H2NMe]W(CH2CMe3)(CCMe3) (11a), [3,4,5-F3C6H2NMe]W(CH2SiMe3)(CSiMe3) (11b), [3-CF3C6H4NMe]Mo(CH2SiMe3)2 (13), [3-CF3C6H4NMe]Mo(CH2CMe3)Cl (14), and [3-CF3C6H4NMe]Mo(CCMe3)(CH2CMe3)

  钼和钨络合物已经制备含有三种不同类型的类型的二酰胺配位体的[（ArNCH 2 CH 2）2 NME] 2 -（[ArNMe] 2 - ，其中Ar = C 6 ˚F 5，3,4,5- -F 3 C 6 H 2，3 -CF 3 C 6 H 4）。[Et 3 NH] [ArNMe] MCl 3 }类型的起始原料是由MCl 4试剂和配位体在加入三乙胺后制得的。[Et 3 NH] [C的X射线研究6 F 5 NMe] MoCl 3 }，[Et 3 NH] [C 6 F 5 NMe] WCl 3 }和[Bu 4 N] [3-CF 3 C 6 H 4 NMe] MoCl 3 }揭示了在变形的伪八面体环境中，酰胺基氮原子彼此之间近似为顺式。向各种[Et 3 NH] [ArNMe] MCl 3 }物种中添加各种烷基化试剂导致形成[C 6 F 5 NMe] MoMe 2（3），[C 6 F 5 NMe]
• Synthesis, characterization, X-ray and electronic structures of diethyl ether and 1,2-dimethoxyethane adducts of molybdenum(<scp>iv</scp>) chloride and tungsten(<scp>iv</scp>) chloride
  作者：Thomas E. Shaw、Timothy J. Diethrich、Charlotte L. Stern、Brian L. Scott、Titel Jurca、Thomas M. Gilbert、Alfred P. Sattelberger

  DOI：10.1039/d2dt00787h

  日期：——

  MoCl4(dme) and WCl4(dme) were developed, and X-ray diffraction data were obtained and analysed. The magnetic properties of the dme adducts were probed, both with Gouy and SQUID magnetometry measurements. The magnetic moment of WCl4(dme) was smaller than that of MoCl4(dme), an observation that we attribute to the greater spin–orbit coupling of tungsten. Electronic structure studies were also conducted to probe

  氯化钼 ( IV ) 和氯化钨 ( IV )的双 (乙醚) 和 1,2-二甲氧基乙烷 (dme) 加合物是各种合成无机和有机金属反应的有价值的起始材料。尽管这些 6 坐标配合物具有广泛的用途和广泛的用途，但它们的合成仍然未经优化，并且在超过 30 年之后它们的表征不完整。在探索反式-MoCl 4 (OEt 2 ) 2的配体交换行为时，我们获得了这种红橙色配合物的单晶，随后将其结构参数与最近报道的反式-WCl 4 (OEt 2) 2。开发了 MoCl 4 (dme) 和 WCl 4 (dme) 的显着改进程序，并获得并分析了 X 射线衍射数据。用 Gouy 和 SQUID 磁强计测量了二甲醚加合物的磁性。WCl 4 (dme)的磁矩小于 MoCl 4 (dme)，我们将这一观察结果归因于钨的更大自旋轨道耦合。还进行了电子结构研究以探测二乙醚加合物的优先反式构型并确定二甲醚加合物的紫外-可见光谱。
• Molybdenum and Tungsten Structural Differences are Dependent on <i>n</i>d<i>_z</i>_²/(<i>n</i> + 1)s Mixing: Comparisons of (silox)₃MX/R (M = Mo, W; silox = <i>^t</i>Bu₃SiO)
  作者：David S. Kuiper、Richard E. Douthwaite、Ana-Rita Mayol、Peter T. Wolczanski、Emil B. Lobkovsky、Thomas R. Cundari、Oanh P. Lam、Karsten Meyer

  DOI：10.1021/ic800139c

  日期：2008.8.1

  Treatment of trans-(Et2O)(2)MoCl4 with 2 or 3 equiv of Na(silox) (i.e., (NaOSiBu3)-Bu-t) afforded (Silox)(3)MoCl2 (1-Mo) or (silox)(3)MoCl (2-Mo). Purification of 2-Mo was accomplished via addition of PMe3 to precipitate (Silox)(3)CIMoPMe3 (2-MoPMe3), followed by thermolysis to remove phosphine. Use of MoCl3(THF)(3) with various amounts of Na(silox) produced (Silox)(2)ClMoMoCl(Silox)(2) (3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (Silox)(3)MoR (R = Me, 2-MoMe; Et, 2-MoEt). 2-MoEt was also synthesized from C2H4 and (Silox)(3)MoH, which was prepared from 2-Mo and NaBEt3H. Thermolysis of WCl6 with (HOSiBu3)-Bu-t afforded (Silox)(2)WCl4 (4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (Silox)(3)WCl2 (1-W, tbp, X-ray), which was alternatively prepared from trans-(Et2S)(2) WCl4 and 3 equiv of Tl(silox). Na/Hg reduction of 1-W generated (silox)(3)WCl (2-W). Alkylation of 2-W with MeMgBr produced (Silox)(3)WMe (2-WMe), which dehydrogenated to (Silox)(3)WCH (6-W) with Delta H-double dagger = 14.9(9) kcal/ mol and Delta S-double dagger = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-T-d (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/ molecular mechanics studies of the S = 0 and S = 1 states for full models of 2-Mo, 2-MoEt, 2-W and 2-WMe corroborate the experimental findings and are consistent with the greater nd(z)(2)/(n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.
• Reduction of tungsten(VI) and molybdenum(V) by allyltrimethylsilane and cyclopentene. Simple high yield syntheses of MoCl4(OEt2)2, MoCl4(dme), WCl4(thf)2, WCl4(dme) and WOCl3(thf)2
  作者：Christina Persson、Carlaxel Andersson

  DOI：10.1016/s0020-1693(00)81663-1

  日期：1993.1

  Convenient high yield methods to prepare MoCl4(OEt2)2, MoCl4(dme), WCl4(thf)2, WCl4(dme) and WOCl3(thf)2 by reduction Of MOCl5 and WCl6, with olefins such as allyltrimethylsilane or cyclopentene are presented.