diphenylpermethylzirconocene | 79847-76-0

• 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: diphenylpermethylzirconocene
• 英文别名: Cp'2Zr(Ph)2
• CAS: 79847-76-0
• 化学式: C₃₂H₄₀Zr
• 分子量: 515.894
• InChiKey: SMGAJJNSHTVIIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.0
• 重原子数：
  33.0
• 可旋转键数：
  2.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  diphenylpermethylzirconocene 在 H₂S 作用下， 以 甲苯 为溶剂， 以63%的产率得到(μ-sulfido)bis{(hydrosulfido)(permethylzirconocene)}
  参考文献：
  名称：

  高反应性中间体Cp * 2Zr：O和Cp * 2Zr：S的生成：与炔烃，腈和衍生物配体的捕集反应

  摘要：

  This paper outlines synthetic procedures that result in the successful generation of the long-sought oxo complex [Cp*2Zr = O] and its sulfur analogue [Cp*2Zr = S]. The generation of [Cp*2Zr = O] has been accomplished at 160-degrees-C by alpha-elimination of benzene from Cp*2Zr(Ph)(OH) (1) and at room temperature by deprotonation of Cp*2Zr(OH)(OSO2CF3) with KN(SiMe3)2. The oxo species reacts with diphenylacetylene and di-p-tolylacetylene to give oxametallacyclobutenes Cp*2Zr(OC(Ph) = C(Ph)) (5a) and (Cp*2Zr(OC-(Tol) = C(Tol)) (5b), which are stable at room temperature. At the elevated temperatures necessary for the alpha-elimination of benzene from 1, however, these complexes rearrange to ortho-metalated oxametallacycles Cp*2Zr(OC(o-C6H4) = C(Ph)(H)) (2a) and Cp*2Zr(OC(o-C6H4CH3) = C(Tol)(H)) (2b), and these are the products isolated in the 160-degrees-C thermolysis of 1. Similarly, generation of [Cp*2Zr = O] at 160-degrees-C in the presence of 1,4-diphenyl-1,3-butadiyne yields the complex metallacycle (eta-5-C5(CH3)5)Zr(OC(Ph) = C(H)- = C (Ph)(eta-5-C5(CH3)4CH2)) (3), in which one Cp* ligand has been integrated into the coordinated enolate moiety. In the presence of excess benzonitrile at both high and low temperature the oxo complex yields the six-membered oxaazametallacycle Cp*2Zr(OC(Ph) = NC(Ph) = N) (4a), formed from insertion of 2 equiv of PhCN into the Zr = O fragment. The connectivities of complexes 2a, 3, and 4a were confirmed by X-ray structure determinations. At room temperature, reaction of [Cp*2Zr = O] with the unsymmetrical alkyne 1-phenyl-1-propyne proceeds regiospecifically, yielding only the metallacycle Cp*2Zr(OC(Me) = C(Ph)) (5d), having the phenyl substituent located alpha to the metal center; this material gives phenylacetone upon hydrolysis. Kinetic, alkyne-exchange, and isotope-labeling studies support a mechanism involving direct elimination of benzene from 1 in the thermal generation of [Cp*2Zr = O]. They also suggest that the rearrangement of the oxametallacyclobutenes 5a,b may proceed by initial reversion of the metallacycle to an oxo-alkyne complex followed by attack of oxygen on the phenyl ring of the alkyne. The isoelectronic sulfido complex [Cp*2Zr = S] is generated by room temperature dehydrohalogenation of Cp*2Zr(SH)(I) (10). In analogy to the earlier generated imido complexes [Cp2Zr = N-R], the sulifido complex can be stabilized and isolated in pure form as the dative ligand adduct [Cp*2(L)Zr = S] (L = pyridine (11a), 4-tert-butylpyridine (11b)). An X-ray structure determination of 11b confirmed the unusual Zr = S bonding mode and represents the first example of this structural type among group 4 metals. Like its oxo analogue, the Zr = S multiply bonded linkage reacts with nitriles and alkynes to form the thiaazametallacycle Cp*2Zr(SC(Ph) = NC(Ph) = N) (12) and the thiametallacyclobutenes Cp*2Zr(SC(R) = C(R)) (13a-c, R = Et, Ph, Tol). The latter structural type was confirmed by an X-ray structure determination of 13b. The thiametallacyclobutenes readily revert to the monomeric terminal sulfido complexes 11 and free alkyne by reaction of the metallacyclobutene with pyridine; with appropriate alkynes and dative ligands, equilibria between the thiametallacyclobutenes and ligand-trapped sulfido complexes can be established and directly observed by NMR spectrometry in solution.Judging from these observations, the sulfido ligand appears to be the most stable linkage in the Zr = X (X = NR, O, S) series.

  DOI：

  10.1021/om00038a040
• 作为产物：
  描述：

  bis(pentamethylcyclopentadienyl)zirconium(IV) dichloride 、 苯基锂 以 乙醚 为溶剂， 以60%的产率得到diphenylpermethylzirconocene
  参考文献：
  名称：

  Photochemical decomposition of (diphenyl)bis(η5-cyclopentadienyl) titanium, (diphenyl)bis(η5-pentamethylcyclopentadienyl) titanium and the zirconium analogs

  摘要：

  DOI：

  10.1016/s0020-1693(00)88596-5

文献信息

• Group 4 Diarylmetallocenes as Bespoke Aryne Precursors for Titanium-Catalyzed [2 + 2 + 2] Cycloaddition of Arynes and Alkynes
  作者：Benjamin R. Reiner、Ian A. Tonks

  DOI：10.1021/acs.inorgchem.9b01082

  日期：2019.8.19

  reports describing titanium (Ti)-catalyzed [2 + 2 + 2] cyclotrimerization of alkynes, the incorporation of arynes into this potent manifold has never been reported. The in situ generation of arynes often requires fluoride, which instead will react with the highly fluorophilic Ti center, suppressing productive catalysis. Herein, we describe the use of group 4 diarylmetallocenes, CpR2MAr2 (CpR = C5H5,

  尽管有大量报道描述了钛（Ti）催化炔烃的[2 + 2 + 2]环三聚反应，但从未报道过将芳烃掺入到这种有效的歧管中。芳烃的原位生成通常需要氟化物，而氟化物将与高度氟的Ti中心反应，从而抑制生产催化。在这里，我们描述了使用第4组二芳基金属茂CpR2MAr2（CpR = C5H5，C5Me5; M = Ti，Zr）作为芳烃前体，通过与2当量的炔烃偶合，进行Ti催化的取代萘的合成。催化剂负载量为1％时，可获得所需萘产品的中等至良好收率，这比钯或镍催化的类似反应低约一个数量级。此外，萘在电子产品，光伏产品，和制药业，敦促发现更多的经济综合体。这些结果表明，芳烃从CpR2M（η2-芳烃）配合物转移到另一种金属是将芳烃片段引入有机金属催化过程的可行途径。
• Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium
  作者：Laurel E. Schock、Tobin J. Marks

  DOI：10.1021/ja00231a020

  日期：1988.11
• Synthesis and characterisation of Group 4 metallocene alkoxide complexes. X-ray crystal structure of Cp*2ZrCl(OCH2CH2SPh)
  作者：Rosa Fandos*、Carolina Hernández、Antonio Otero*、Ana Rodrı́guez、Maria José Ruiz、Pilar Terreros

  DOI：10.1016/s0022-328x(00)00336-3

  日期：2000.7

  Halo-alkoxide zirconocene complexes (eta(5)-C5Me5)(2)ZrCl(OCH2CH2SPh) (1) and (eta(5)-C5Me5)(2)ZrCl(OC6H4SH) (2) have been prepared by reaction of the corresponding zirconocene dichloride with HOCH2CH2SPh or HOC6H4SH, respectively, in the presence of NEt3. The molecular structure of 1 has been determined by X-ray diffraction studies. Alkyl- and aryl-containing species (eta(3)-C5Me5)(2)ZrMe(OCH2CH2SPh) (3) and (eta(5)-C5Me5)(2)ZrPh(OCH2CH2SPh) (4) were synthesised by reaction of the corresponding dialkyl or diaryl species with HOCH2CH2SPh, or by reaction of complex I with LiMe or LiPh, respectively. Finally, the dialkoxide complexes L2M(OCH2CH2SR)(2) [L = eta(5)-C5H5, M = Ti, R = Ph (5); L = eta(5)-C5Me5, M = Ti, R = Ph (6); L = eta(5)-C5Me5, M = Ti, R = Me (7)] were prepared by reaction of the appropriate dichloride and alcohol in the presence of NEt3, and (eta(5)-C5H5)(2)Zr(OCH2CH2SMe)(2) (8) was synthesised by reacting (eta(5)-C5H5)(2)ZrMe2 with two equivalents of HOCH2CH2SMe. (C) 2000 Elsevier Science S.A. All rights reserved.
• Schock, Laurel E.; Brock, Carolyn P.; Marks, Tobin J., Organometallics, 1987, vol. 6, # 2, p. 232 - 241
  作者：Schock, Laurel E.、Brock, Carolyn P.、Marks, Tobin J.

  DOI：——

  日期：——