bis(trimethylphosphine)bis(6,6-dimethylcyclohexadienyl)zirconium(II) | 628738-02-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: bis(trimethylphosphine)bis(6,6-dimethylcyclohexadienyl)zirconium(II)
• 英文别名: Zr(6,6-dimethylcyclohexadienyl)₂(N(CH₃)₃)₂；Zr(η5-6,6-dimethylcyclohexadienyl)2(PMe3)2；[Zr(6,6-dimethylcyclohexadienyl)2(PMe3)2]；Zr(6,6-dimethylcyclohexadienyl)2(PMe3)2；Zr(6,6-dmch)2(PMe3)2；5,5-dimethylcyclohexa-1,3-diene;trimethylphosphane;zirconium(2+)
• CAS: 628738-02-3
• 化学式: C₂₂H₄₀P₂Zr
• 分子量: 457.731
• InChiKey: HTJGECATVCGZFI-UHFFFAOYSA-N

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：

  bis(trimethylphosphine)bis(6,6-dimethylcyclohexadienyl)zirconium(II) 、 styryltrimethylsilane 以 正己烷 为溶剂， 以49%的产率得到Zr(6,6-dimethylcyclohexadienyl)2(1-phenyl-2-trimethylsilylacetylene)2
  参考文献：
  名称：

  The reaction of the bis(6,6-dimethylcyclohexadienyl)zirconium fragment with PhC2SiMe3 – A 5+2+2 ring construction

  摘要：

  The reaction of the edge-bridged open zirconocene, Zr(6,6-dmch)(2)(PMe3)(2) (dmch = dimethylcyclohexadienyl) with two equivalents of PhC2SiMe3 leads to a 5 + 2 + 2 ring construction, resulting in a 4.3.1 bicyclodecadienyl skeleton. The resulting complex, with eta(3)-allyl, eta(4)-diene, and eta(5)-dienyl coordination, has a formal 16 electron configuration, and contains close contacts between the metal center and two lengthened C-C bonds, indicative of weak agostic interactions. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2008.04.001
• 作为产物：
  描述：

  6,6-dimethylcyclohexadienyl potassium 、 氯化锆(IV) 、 三甲基膦 以 四氢呋喃 为溶剂， 以60%的产率得到bis(trimethylphosphine)bis(6,6-dimethylcyclohexadienyl)zirconium(II)
  参考文献：
  名称：

  Synthesis and structure of the edge-bridged open zirconocene, Zr(6,6-dmch)2(PMe3)2 (dmch=dimethylcyclohexadienyl), and its imine coupling product

  摘要：

  The reaction of ZrCl4 with four equivalents of the 6,6-dimethylcyclohexadienyl anion (6,6-dmch(-)) in the presence of PMe3 leads to the 18 electron Zr(6,6-dmch)(2)(PMe3)(2). This complex was found to undergo a coupling reaction with two equivalents of PhCH = NPh, such that the couplings involved the two termini of the same dienyl ligand, yielding a formal Zr(eta(5)-dienyl)(eta(3)-allyl)(pi-amide)(2) complex. Both metal complexes have been structurally characterized. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00408-x

文献信息

• Syntheses and Structural Studies of the Coupling Products of the Zr(6,6-dimethylcyclohexadienyl)2 Fragment with the Diimines (CH2) n [N=CH(C6H5)]2 (n = 3,4)
  作者：Rehan Basta、Atta M. Arif、Richard D. Ernst

  DOI：10.1007/s10870-012-0389-3

  日期：2013.2

  The reactions of the α,ω-diimines (CH2) n [N=CH(C6H5)]2 with Zr(6,6-dmch)2(PMe3)2 (dmch = dimethylcyclohexadienyl) lead to couplings of both imine carbon atoms, each to one of a single dmch ligand’s termini, which thereby also leads to the formation of two Zr–N bonds, and release of the phosphine ligands. The resulting complexes possess 18 electron configurations by virtue of a remaining η5-6,6-dmch ligand, η3-allyl coordination by the coupled 6,6-dmch ligand, and π-amide coordination by each nitrogen donor center. The η5-6,6-dmch ligand displays the distortions expected for a high valent metal pentadienyl complex. The n = 3 complex crystallized in the monoclinic space group P21/c with a = 8.5687(2) Å, b = 27.8768(6) Å, c = 11.7747(3) Å, β = 103.6081(8)°, V = 2,733.64(11) Å3, Dcalc = 1.351 g/cm3 at 150(1) K. For the n = 4 complex, the triclinic space group P $$ \overline1} $$ is adopted, with a = 11.1279(3) Å, b = 11.3846(3) Å, c = 14.9154(3) Å, α = 81.6030(13)°, β = 69.8503(13)°, γ = 84.6588(12)°, V = 1,753.05(7) Å3, Dcalc = 1.283 g cm−3 at 150(1) K. The reactions of the Zr(6,6-dimethylcyclohexadienyl)2 fragment with α,ω-diimines (CH2) n [N=CH(C6H5)]2 led to couplings between the imine carbon atoms and the dienyl termini, thereby resulting in 12- and 13-membered ring constructions.

  nbsp;Å, β = 103.6081(8)°, V = 2,733.64(11) Å3, Dcalc = 1.351 g/cm3 at 150(1) K. 对于n = 4复合物，采用三斜晶系空间群P $$ \overline1} $$，a = 11.1279(3) Å，b = 11.3846(3) Å，c = 14.9154(3) Å，β = 103.
• Syntheses and characterization of mono(6,6-dimethylcyclohexadienyl) complexes of titanium and zirconium
  作者：Atta M. Arif、Rehan Basta、Richard D. Ernst

  DOI：10.1016/j.poly.2005.09.026

  日期：2006.3

  Reactions of appropriate bis(6,6-dmch) (dmch = dimethylcyclohexadienyl) complexes of titanium(II) or zirconium(IV) with dichloroethane or phosphines, respectively, have led to loss of one dienyl ligand, and the formation of mono(6,6-dmch) complexes of Ti(III) or Zr(IV). The polymeric [Ti(6,6-dmch)Cl-2](n) and Zr(6,6-dmch)Br-3(dmpe) (dmpe = 1,2-bis(dimethylphosphino)ethane) have thus been isolated, and fully characterized. (c) 2005 Elsevier Ltd. All rights reserved.
• Reactions of Zr(C5H5)(6,6-dmch)(PMe3)2 and Zr(6,6-dmch)2(PMe3)2 (dmch=dimethylcyclohexadienyl) with CO and alkynes
  作者：Rehan Basta、Benjamin G. Harvey、Atta M. Arif、Richard D. Ernst

  DOI：10.1016/j.ica.2004.04.012

  日期：2004.11

  The reactions of Zr(C5H5)(6,6-dmch)(PMe3)(2) and Zr(6,6-dmch)(2)(PMe3)(2) (dmch = dimethylcyclohexadienyl) with CO lead to the selective replacement of one PMe3 ligand by CO. Both carbonyl complexes have been structurally characterized. Additionally, the reaction of the latter complex with PhC2SiMe3 leads to a similar replacement of one PMe3 ligand, involving simple coordination of the alkyne, rather than any coupling to the dmch ligand. (C) 2004 Elsevier B.V. All rights reserved.
• Higher Valent Metal Pentadienyl Chemistry:  Syntheses, Structures, and Reactions of Zr(6,6-dmch)₂X₂ Complexes (dmch = dimethylcyclohexadienyl; X = Cl, Br, I) and Related Species
  作者：Rehan Basta、Atta M. Arif、Richard D. Ernst

  DOI：10.1021/om058017j

  日期：2005.8.1

  The zirconium(II) complex Zr(6,6-dmch)(2)(PMe3)(2) undergoes facile reactions with 1,2-dihaloalkanes, yielding the formal oxidative addition products Zr(6,6-dmch)(2)X-2 (X = Cl, Br, I). A similar reaction with 1-chloro-2-methoxyethane yields Zr(6,6-dmch)(2)(Cl)(OCH3). Each of the complexes has been characterized analytically, spectroscopically, and structurally. A direct oxidative addition reaction occurs with CH3Br, yielding the thermally unstable Zr(6,6-dmch)(2)(CH3)(Br), which has been characterized spectroscopically and structurally. As had been observed for related Zr(C5H5)(6,6-dmch)X-2 complexes, the Zr-dmch coordination is severely skewed, with quite short Zr-C3 interactions and substantially lengthened interactions with the remaining carbon atoms of the dienyl fragment. This may be attributed to an inability of the contracted Zr(IV) orbitals to interact effectively with all the carbon atoms in the wide, electronically open dienyl ligands.