(η(5)-C5H5)Mo(CH2C6H5)(η(2)-PhC2Ph)(P(OMe)3) | 182122-01-6

• 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: (η(5)-C5H5)Mo(CH2C6H5)(η(2)-PhC2Ph)(P(OMe)3)
• 英文别名: cyclopenta-1,3-diene;methanidylbenzene;molybdenum(2+);2-phenylethynylbenzene;trimethyl phosphite
• CAS: 182122-01-6
• 化学式: C₂₉H₃₁MoO₃P
• 分子量: 554.477
• InChiKey: MMEIFQZFXXUVFE-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：

  (η(5)-C5H5)Mo(CH2C6H5)(η(2)-PhC2Ph)(P(OMe)3) 、 二苯基乙炔 以 苯 为溶剂， 以50%的产率得到(η(5)-C5H5)Mo(η(6)-C6Ph6)
  参考文献：
  名称：

  Redox properties of the 17-electron sandwich (η5-C5H5)Mo(η6-C6Ph6): electrochemical characterization of the 16 e− Lewis acid monocation and its PF6− adduct

  摘要：

  Thermolysis of CpMo(CH2C6H5)(eta(2)-PhC2Ph)[P(OMe)(3)] [Cp = (eta(5)-C5H5)] unexpectedly gives the mixed-sandwich 17-electron metallocene CpMo(eta(6)-C6Ph6), 1. The title compound undergoes reversible one-electron oxidation (E-1/2 = - 0.25 V vs. ferrocene) and reduction (E-1/2 = - 2.02 V) reactions which were characterized by voltammetry and coulometry. When the oxidation of 1 is accomplished in CH2Cl2/[Bu4N][PF6] electrolyte, the 16 e(-) Mo(II) complex 1(+) is in equilibrium with a thermodynamically-favored product formulated as the [PF6](-) adduct, 1-FPF5, 3. Adduct 3 remains intact upon further one-electron oxidation to the Mo(III) complex 3(+), but it rapidly releases [PF6](-) when reduced to the Mo(I) species 3(-). Other counterions such as [BF4](-) and [ClO4](-) do not show the same degree of interaction with the 16 e(-) Mo(II) cation. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)01038-9
• 作为产物：
  描述：

  η5-cyclopentadienyl(diphenylacetylene)bis(trimethyl phosphite)molybdenum tetrafluoroborate 、 苄基氯化镁 以 四氢呋喃 为溶剂， 以84%的产率得到(η(5)-C5H5)Mo(CH2C6H5)(η(2)-PhC2Ph)(P(OMe)3)
  参考文献：
  名称：

  Redox properties of the 17-electron sandwich (η5-C5H5)Mo(η6-C6Ph6): electrochemical characterization of the 16 e− Lewis acid monocation and its PF6− adduct

  摘要：

  Thermolysis of CpMo(CH2C6H5)(eta(2)-PhC2Ph)[P(OMe)(3)] [Cp = (eta(5)-C5H5)] unexpectedly gives the mixed-sandwich 17-electron metallocene CpMo(eta(6)-C6Ph6), 1. The title compound undergoes reversible one-electron oxidation (E-1/2 = - 0.25 V vs. ferrocene) and reduction (E-1/2 = - 2.02 V) reactions which were characterized by voltammetry and coulometry. When the oxidation of 1 is accomplished in CH2Cl2/[Bu4N][PF6] electrolyte, the 16 e(-) Mo(II) complex 1(+) is in equilibrium with a thermodynamically-favored product formulated as the [PF6](-) adduct, 1-FPF5, 3. Adduct 3 remains intact upon further one-electron oxidation to the Mo(III) complex 3(+), but it rapidly releases [PF6](-) when reduced to the Mo(I) species 3(-). Other counterions such as [BF4](-) and [ClO4](-) do not show the same degree of interaction with the 16 e(-) Mo(II) cation. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)01038-9

文献信息

• Reaction of the η²(4e)-donor alkyne complexes [Mo{η²(4e)-R¹C₂R²}{P(OMe)₃}₂(η-C₅H₅)](R¹= R²= Ph or Me; R¹= Me, R²= Ph) with the Grignard reagents MgR³(X)(R³= Me, Et, CH₂Ph, CH₂CHCH₂or CHCH₂) and CH₂(MgI)₂
  作者：Georg Brauers、Frank J. Feher、Michael Green、John K. Hogg、A. Guy Orpen

  DOI：10.1039/dt9960003387

  日期：——

  Reaction of the complex [Moeta(2)(4e)-PhC(2)Ph}P(OMe)(3)}(2)(eta-C5H5)][BF4]1 with MgR(X) (R = Me, Et or PhCH(2)) afforded good yields of [Moeta(2)(4e)-PhC(2)Ph}RP(OMe)(3)}(eta-C5H5)]. Unexpectedly, reaction of 1 with the 1,1-di-Grignard reagent CH2(MgI)(2) gave the X-ray crystallographically identified zwitterionic complex [Moeta(2)(4e)-PhC(2)Ph}eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)], similar reactions with the but-2-yne and 1-phenylprop-2-yne complexes affording the analogous [Moeta(2)(4e)-RC(2)R(2))eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] (R = R(2) = Me; R = Me, R(2) = Ph). Treatment of the zwitterionic diphenylacetylene- and 1-phenylprop-2-yne-substituted complexes with K[BHBu(3)(s)] gave the anionic eta(2)(3e)-vinyl complexes K[Mo=C(R)CH(Ph)}eta(2)-P(OMe)(2)OBF2OP(OMe)(2)(eta-C5H5)] (R = Ph or Me). Protonation (HBF4 . Et(2)O) of the diphenyl-substituted eta(2)(3e)-vinyl complex followed by addition of carbon monoxide, trimethyl phosphite, or diphenylacetylene afforded trans-stilbene and the complexes [Mo(CO)(2)eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta(2)-C5H5)], [MoP(OMe)(3)}(2)eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] and [Moeta(2)(4e)-PhC(2)Ph}eta(2)P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] respectively. When CH2=CHCH2MgBr was added to 1 an unstable compound was formed, which on addition of P(OMe)(3) gave [Moeta(3)-C(Ph)=C(Ph)CH2CH=CH2}P(OMe)(3)}(2)(eta-C5H5)], the identity of which was confirmed by X-ray crystallography. This reaction is explained in terms of an unusual metalla-3,3-sigmatropic shift process. A similar reaction between 1 and CH2=CHMgBr followed by addition of P(OMe)(3) surprisingly gave the eta(3)-cyclopropenyl complex [Mo(eta(3)-C(3)Ph(2)Me)P(OMe)(3)}(2)(eta-C5H5)]. The complex [Moeta(2)(4e)-PhC(2)Ph}MeP(OMe)(3)}(eta-C5H5)] reacted thermally (78 degrees C) with an excess of PhC(2)Ph to give the X-ray crystallographically identified complex [MoH(eta(4)-C(5)H(2)Ph(4))P(OMe)(3)}(eta-C5H5)], which on heating (100 degrees C) afforded the dihydride [MoH2(eta(5)-C(5)HPh(4))(eta-C5H5)].