VCl3(PMePh2)2 | 97704-59-1

• 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: VCl3(PMePh2)2
• CAS: 97704-59-1
• 化学式: C₂₆H₂₆Cl₃P₂V
• 分子量: 557.74
• InChiKey: WSSUPJVMWOLNKM-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  VCl3(PMePh2)2 、 1-trimethylsilyl-2,2-dimethylhydrazine 以 乙腈 为溶剂， 以20%的产率得到
  参考文献：
  名称：

  Reactions of substituted hydrazines with vanadium(III) compounds: crystal structures of [NH₂Me₂]₂[(VCl₃)₂(µ-NNMe₂)₃], [V(OC₆H₃Prⁱ₂-2,6)₃(NH₂NMe₂)₂] and [V(OC₆H₃Prⁱ₂-2,6)₃(NH₂NMePh)₂]

  摘要：

  Reaction of Me(3)SiNHNMe(2) with [VCl3(PMePh(2))(2)] or [VCl3(thf)(3)] (thf = tetrahydrofuran) gave the triply hydrazide-bridged complex [NH(2)Me(2)](2)[(VCl3)(2)(mu-NNMe(2))(3)] 1 the crystal structure of which has been determined. Cyclic voltammetry shows 1 to have E(1/2)(ox) = 0.30 V (reversible at -35 degrees C) and E(2)(ox) = 1.35 V (vs. ferrocene-ferrocenium). Cation exchange gave [PPh(4)](2)[(VCl3)(2)(mu-NNMe(2))(3)] and reaction with Li(SC6H2Pr3i-2,4,6) gave [NH(2)Me(2)](2)[{V(SC6H2Pr3i-2,4,6)(3)}(2)(mu-NN(2)Me(2))(2)]. Treatment of [V(OC6H3Pr2i-2,6)(4)Li(thf)] with NH(2)NMe(2) gave the low-melting compound [V(OC6H3Pr2i-2,6)(3)(NH(2)NMe(2))(2)], shown by astructure determination to be essentially trigonal bipyramidal, with axial hydrazine ligands. The analogue [V(OC6H3Pr2i-2,6)(3)(NH(2)NMePh)(2)] has also been prepared and shown to have a similar structure.

  DOI：

  10.1039/dt9960002755

文献信息

• [EN] PHOSPHINIC VANADIUM COMPLEX, CATALYTIC SYSTEM COMPRISING SAID PHOSPHINIC VANADIUM COMPLEX AND PROCESS FOR THE (CO) POLYMERIZATION OF CONJUGATED DIENES<br/>[FR] COMPLEXE DE VANADIUM PHOSPHINIQUE, SYSTÈME CATALYTIQUE COMPRENANT LEDIT COMPLEXE DE VANADIUM PHOSPHINIQUE ET PROCÉDÉ DE (CO)POLYMÉRISATION DE DIÈNES CONJUGUÉS
  申请人：VERSALIS SPA

  公开号：WO2016128812A1

  公开（公告）日：2016-08-18

  Vanadium phosphinic complex having general formula (I) or (II): V(X)M3P^WFys-nMO V(X)3[(R3)2P(R4)P(R3)2] (ID wherein: X represents an anion selected from halogens such as, for example, chlorine, bromine, iodine, preferably chlorine; or is selected from the following groups: thiocyanate, isocyanate, sulfate, acid sulfate, phosphate, acid phosphate, carboxylate, dicarboxylate; Ri, identical or different among them, represent a hydrogen atom, or an allyl group (CH2 = CH-CH2-); or are selected from alkyl groups CrC2o, preferably CrC^, linear or branched, optionally halogenated, optionally substituted cycloalkyl groups; - n is an integer ranging from 0 to 3; R2, identical or different among them, are selected from optionally substituted aryl groups; R3, identical or different among them, represent a hydrogen atom, or an allyl group (CH2 = CH-CH2-); or are selected from alkyl groups C1-C2o, preferably CrC^, linear or branched, optionally halogenated, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R4 represents a group -NR5 wherein R5 represents a hydrogen atom, or is selected from C1-C20 alkyl groups, preferably CrC15, linear or branched; or R4 represents an alkylene group - (CH2) p- wherein p represents an integer ranging from 1 to 5; provided that in the general formula (I), in case n is equal to 1 and Ri is methyl, R2 is different from phenyl. Said phosphinic vanadium complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

  钒膦配合物的一般化学式（I）或（II）为：V（X）M3P^WFys-nMO V（X）3[(R3)2P(R4)P(R3)2]（其中：X代表从卤素中选择的阴离子，例如氯、溴、碘，优选氯；或从以下组中选择：硫氰酸根、异氰酸根、硫酸根、酸性硫酸根、磷酸根、酸性磷酸根、羧酸根、二羧酸根；Ri，相同或不同，代表氢原子或烯丙基（CH2 = CH- -）；或从烷基CrC2o中选择，优选CrC^，线性或支链，可选择卤代，可选择取代的环烷基；- n是一个从0到3的整数；R2，相同或不同，从可选择取代的芳基中选择；R3，相同或不同，代表氢原子或烯丙基（ = CH- -）；或从烷基C1-C2o中选择，优选CrC^，线性或支链，可选择卤代，可选择取代的环烷基，可选择取代的芳基；R4代表一个基团-NR5，其中R5代表氢原子，或从C1-C20烷基中选择，优选CrC15，线性或支链；或R4代表一个烷基基团-( ) p-，其中p代表一个从1到5的整数；在一般化学式（I）中，如果n等于1且Ri为甲基，则R2与苯基不同。具有一般化学式（I）或（II）的膦钒配合物可有利地用于共轭二烯的（共）聚合的催化系统中。
• The preparation and crystal and molecular structures of trichlorobis(methyldiphenylphosphine)vanadium(III) and its acetonitrile adduct
  作者：John Bultitude、Leslie F. Larkworthy、David C. Povey、Gallienus W. Smith、Jonathan R. Dilworth

  DOI：10.1039/dt9860002253

  日期：——

  the crystal there are two independent trigonal-bipyramidal molecules with axial phosphine ligands. There is considerable distortion from regular co-ordination polyhedra and mean bond distances are V–Cl, 2.22 and 2.23 Å and V–P, 2.54 and 2.53 Å. On long reflux of a solution of [VCl3(MeCN)3] and PPh2Me in toluene, the complex [VCl3(MeCN)(PPh2Me)2] is obtained. It contains six-co-ordinate vanadium(III)

  络合物[VCl 3（PPh 2 Me）2 ]是由[VCl 3（MeCN）3 ]或[VCl 3（thf）3 ]（thf =四氢呋喃）和叔膦在甲苯中制得的。在晶体中，有两个独立的具有轴向膦配体的三角双锥体分子。规则配位多面体会产生相当大的畸变，平均键距为V–Cl，2.22和2.23Å，以及V–P，2.54和2.53Å。在[VCl 3（MeCN）3 ]和PPh 2 Me的甲苯溶液中长时间回流后，络合物[VCl 3（MeCN）（PPh 2 Me）2获得。它含有六配位的钒（III），其子午线V–Cl键的平均长度为2.30Å。其他键距为V–N，2.140（3）Å和V–P，2.56Å（av。）。
• Vanadium(III)–catalyzed copolymerization of ethylene with norbornene: Microstructure at tetrad level and reactivity ratios
  作者：Giuseppe Leone、Ivana Pierro、Giorgia Zanchin、Alessandra Forni、Fabio Bertini、Arnaldo Rapallo、Giovanni Ricci

  DOI：10.1016/j.molcata.2016.09.002

  日期：2016.12

  activity of VCl3(THF)3 was slightly higher than that of VCl3(PMePh2)2 likely due to a different competition of re-insertion rate of dissociated ligand compared to the insertion/coordination of (co)monomers. Copolymers obtained at low norbornene feedstock concentration from VCl3(THF)3, showed greater non-uniformity in terms of composition distribution with respect to those from VCl3(PMePh2)2 because of

  摘要 合成了带有PMePh2 配体的钒(III) 配合物，对其进行了充分表征，并研究了乙烯与降冰片烯与铝化合物如甲基铝氧烷(MAO) 和Et2AlCl 的均聚和共聚。结果与在存在和不存在三氯乙酸乙酯 (ETA) 和游离膦的情况下用 VCl3(THF)3 和 VCl3 获得的结果进行了仔细比较。VCl3(PMePh2)2 可能通过解离机制被激活，其中不稳定的膦配体的解离是第一步，也可能是速率决定步骤。VCl3(THF)3 的活性略高于VCl3(PMePh2)2 的活性，这可能是由于与(共)单体的插入/配位相比，解离配体的重新插入速率的竞争不同。由 VCl3(THF)3 在低降冰片烯原料浓度下获得的共聚物在组成分布方面表现出比从 VCl3(PMePh2)2 获得的共聚物更大的不均匀性，因为在半间歇聚合过程中组成漂移更明显。这强烈影响了共聚物的热性能，来自 VCl3(PMePh2)2 的共聚物表现出更高的
• Floc'h, Christine Le; Henderson, Richard A.; Hughes, David L., Journal of the Chemical Society. Chemical communications, 1993, # 2, p. 175 - 176
  作者：Floc'h, Christine Le、Henderson, Richard A.、Hughes, David L.、Richards, Raymond L.

  DOI：——

  日期：——
• Bansemer, Rick L.; Huffman, John C.; Caulton, Kenneth G., Inorganic Chemistry, 1985, vol. 24, # 19, p. 3003 - 3006
  作者：Bansemer, Rick L.、Huffman, John C.、Caulton, Kenneth G.

  DOI：——

  日期：——