(η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3 | 149612-77-1

• 英文名称: (η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3
• CAS: 149612-77-1
• 化学式: C₂₃H₄₇Cl₃P₂Si₂Zr
• 分子量: 639.328
• InChiKey: UAJQVUFRCUWDIP-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (2,2-二甲基丙基)锂 、 (η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3 以 甲苯 为溶剂， 以72%的产率得到[η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]Zr(CH2C(CH3)3)3
  参考文献：
  名称：

  Mechanistic Studies of the Formation of Zirconium Alkylidene Complexes [η⁵-C₅H₃-1,3-(SiMe₂CH₂PPrⁱ₂)₂]ZrCHR(Cl) (R = Ph, SiMe₃)

  摘要：

  The reaction of [P2Cp]ZrCl3 (1) with 2 equiv of KCH2Ph generates an equilibrium mixture of alkyl complexes consisting of [P2Cp]ZrCl2(CH2Ph) (2), [P2Cp]ZrCl(CH2Ph)(2) (3), and [P2Cp]Zr(CH2Ph)(3) (4). Thermolysis of this mixture yields the alkylidene complex [P2Cp]Zr=CHPh(Cl) (5) in 85% overall yield. Kinetic studies reveal a composite mechanism that incorporates the above preequilibrium, followed by an intramolecular alpha-abstraction reaction of dibenzyl 3 which follows a first-order rate, with the rate parameters Delta H double dagger = 19(1) kcal mol(-1) and Delta S double dagger = -22(5) cal(-1) mol K-1. A kinetic isotope effect of 3.0(5) was measured at 70 degrees C for the perdeuterated analogue [P2Cp]ZrCl(CD2C6D5)2. The reaction of 1 with 2 equiv of LiCH2-EMe3 (E = C, Si) produces a similar equilibrium mixture as observed for the benzyl analogues, consisting of [P2Cp]ZrCl2(CH2EMe3) (7), [P2Cp]Zr(CH2EMe3)(3) (8), and [P2Cp]ZrCl(CH2EMe3)(2) (9). Thermolysis of this mixture yields [P2Cp]Zr=CHEMe3(Cl) (6). A kinetic analysis conducted on 9 (E = Si) indicated a first-order reaction from which the activation parameters Delta H double dagger = 6(1) kcal mol(-1) and Delta S double dagger = -62(5) cal mol(-1) K-1 were obtained. The results indicate that reaction rates follow the order CH2Ph > CH2SiMe3 > CH2CMe3, an exact reversal of the trend for the homoleptic Ta systems Ta(CH2R)(5). The role of phosphine coordination is discussed to account for this trend. A crystal structure determination obtained for 6b reveals an alpha-agnostic interaction and a structure analogous to that of 5.

  DOI：

  10.1021/ja982969h
• 作为产物：
  描述：

  [(η(5)-C5H3-1,3-(SiMe2CH2P(i-Pr)2)2)Li] 、 以 甲苯 为溶剂， 以93%的产率得到(η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3
  参考文献：
  名称：

  Synthesis, structure and fluxional behavior of [ν5-C5H3-1,3-(SiMe2CH2PPri202[ZrCl3−x Rx(R = Me, CH2Ph, x = 0, 1, 3)

  摘要：

  The addition of the potentially tridentate ligand [P(2)Cp]Li ([P(2)Cp]Li = (eta(5)-C5H3-1,3-(SiMe(2)CH(2)PPr(2)(i))(2))Li) to ZrCl4(THT)(2) (THT = tetrahydrothiophene) generates [P(2)Cp]ZrCl3. The X-ray crystal structure of this compound is described; crystals are orthorhombic, space group P2(1)2(1)2(1) having a = 14.282(2), b = 15.877(3), and c = 13.791(3) Angstrom, Z = 4; the structure was solved by the Patterson method and was refined by full-matrix least-squares to R = 0.032 and R(w) = 0.027 for 2907 reflections with I greater than or equal to 3 sigma(I). The solution behavior of this compound is consistent with the solid state structure in that the phosphine arms of the ligand remain coordinated. Alkylation of [P(2)Cp]ZrCl3 generates the corresponding alkyl complexes [P(2)Cp]ZrCl(3-x)R(x) (x = 1 or 3). In solution [P(2)Cp]Zr(CH(2)Ph)(3) exists in a four-coordinate pseudo-tetrahedral geometry with the two phosphine arms dangling. However, at low temperatures the complexes [P(2)Cp]ZrCl2(CH(2)Ph) and [P(2)Cp]ZrMe(3) exist as five-coordinate trigonal-bipyramidal structures with one phosphine coordinated and one phosphine uncoordinated. In these five-coordinate complexes, the coordinated phosphine exchanges with the uncoordinated phosphine via a dissociative pathway and/or an associative pathway depending on the number of hydrocarbyl substituents. The fluxional behavior of these complexes was studied by variable temperature P-31{H-1}, C-13{H-1} and H-1 NMR spectroscopy, and activation parameters were estimated.

  DOI：

  10.1016/0277-5387(94)00400-9

文献信息

• Formation and reactivity of the zirconium ethylene complexes [η⁵-C₅H₃-1,3-(SiMe₂CH₂PR₂)₂]Zr(η²-CH₂=CH₂)(X) (R = Me, Pr<i>ⁱ</i>; X = Br, C₅H₅)
  作者：Michael D Fryzuk、Paul B Duval、Steven J Rettig

  DOI：10.1139/v00-154

  日期：2001.5.1

  The formation and reactivity of the zirconium ethylene complexes ^R[P₂Cp]Zr(η²-CH₂=CH₂)(X) (2a: R = Prⁱ, X = Br; 2b: R = Me, X = Br; 4a: R = Prⁱ, X = C₅H₅; ^R[P₂Cp] = (η⁵-C₅H₃-1,3-(SiMe₂CH₂PR₂)₂)) are described. Ethylene complexes 2a and 2b are prepared from a reaction of ^R[P₂Cp]ZrCl₃ (1a: R = Prⁱ; 1b: R = Me) with 2 equiv of EtMgBr, presumably via β-H elimination from the diethyl intermediate ^R[P₂Cp]ZrCl(CH₂CH₃)₂. The structure of 2b was determined by X-ray crystallography. Addition of carbon monoxide to 16-electron 2 displaces the ethylene ligand to generate the carbonyl complex ^R[P₂Cp]Zr(CO)₂Br (5a: R = Prⁱ; 5b: R = Me), which is stable only under an atmosphere of CO. The corresponding CO reaction with 18-electron 4a to give the metallocene monocarbonyl analogue ^Pr[P₂Cp]Zr(η⁵-C₅H₅)(CO) (6a) is considerably slower. 2a exhibits fluxional exchange of one carbonyl ligand with bulk ¹³CO in solution; the kinetic parameters for this exchange process are ΔH ^‡ = 9.2(5) kcal mol^–1 and ΔS ^‡ = –17(2) cal mol^–1 K^–1. The addition of diphenylacetylene to 2a yields the alkyne complex ^Pr[P₂Cp]Zr(η²-PhCCPh)Br (7a), which exists in solution as two isomers in equilibrium. A solid-state X-ray structure determination for the minor isomer syn-7a was performed.Key words: zirconium, cyclopentadienyl phosphine, alkyne, metallocyclopropane.

  本文介绍了锆乙烯配合物^R[P₂CP]Zr(η²-CH₂=CH₂)(X) (2a: R = Prⁱ, X = Br; 2b: R = Me, X = Br; 4a: R = Prⁱ, X = C₅H₅; ^R[P₂CP] = (η⁵-C₅H₃-1,3-(SiMe₂CH₂PR₂)₂))的形成和反应。乙烯配合物2a和2b是通过^R[P₂CP]ZrCl₃ (1a: R = Prⁱ; 1b: R = Me)与2当量的EtMgBr反应制备的，可能通过从二乙基中间体^R[P₂CP]ZrCl(CH₂CH₃)₂进行β-H消除而得到。乙烯配合物2b的结构通过X射线衍射法确定。将一氧化碳加到16电子2中，可以将乙烯配体置换为产生稳定的羰基配合物^R[P₂CP]Zr(CO)₂Br (5a: R = Prⁱ; 5b: R = Me)，但只在CO气氛下稳定。相应的CO反应与18电子4a生成的是金属环单羰基类似物^Pr[P₂CP]Zr(η⁵-C₅H₅)(CO) (6a)，反应速度较慢。溶液中的2a表现出一个羰基配体与大量¹³CO的流动交换；这个交换过程的动力学参数为ΔH ^‡ = 9.2(5) kcal mol^–1和ΔS ^‡ = –17(2) cal mol^–1 K^–1。将二苯乙炔加入2a中，可以得到炔配合物^Pr[P₂CP]Zr(η²-PhCCPh)Br (7a)，在溶液中存在两个平衡的异构体。对于次要异构体syn-7a进行了固态X射线结构测定。关键词：锆，环戊二烯基膦，炔，金属环丙烷。