{Pd(η3-methylallyl)(2-(diphenylphosphino)pyridine)Cl} | 135973-14-7

• 英文名称: {Pd(η3-methylallyl)(2-(diphenylphosphino)pyridine)Cl}
• 英文别名: Pd(η3-2-CH3C3H4)Cl(PPh2py)；[PdCl(η3-2-CH3-C3H4)(2-pyridyldiphenylphosphine)]
• CAS: 135973-14-7
• 化学式: C₂₁H₂₁ClNPPd
• 分子量: 460.251
• InChiKey: VHVUOYCONPOWKF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  甲烷磺酸 、 {Pd(η3-methylallyl)(2-(diphenylphosphino)pyridine)Cl} 以 二氯甲烷-D2 为溶剂， 生成 [PdCl(η3-2-CH3-C3H4)(2-pyridyldiphenylphosphine(+1H))][CH3SO3]
  参考文献：
  名称：

  Protonation of palladium(II)-allyl and palladium(0)-olefin complexes containing 2-pyridyldiphenylphosphine

  摘要：

  The pendant nitrogen atom of the Ph2PPy ligand in the Pd(II)-allyl complexes [PdCl(eta(3)-2-CH3C3H4)( Ph2PPy)] (1) and [Pd(eta(3)-2-CH3-C3H4)(Ph2PPy)(2)]BF4 (3) has been protonated with methanesulfonic acid to afford the corresponding pyridinium salts [PdCl(eta(3)-2-CH3-C3H4)(Ph2PPyH)](CH3SO3) (1a) and [Pd(eta(3)-2-CH3-C3H4)(Ph2PPyH)(2)](CH3SO3)(2)(BF4) (3a).Protonation strongly influences the H-1 and C-13 NMR spectral parameters of the allyl moieties of 1a and 3a whose signals resonate at lower fields with respect to the parent species indicating that upon protonation Ph2PPy becomes a weaker sigma-donor and a stronger Pi-acceptor. The allyl moiety, which in 1 is static, becomes dynamic in 1a, the observed syn-syn and anti-anti exchange being due to deligation of the protonated phosphine from the metal centre. Treatment of complex 3 with diethylamine in the presence of fumaronitrile gives the new Pd(0)-olefin complex [Pd(eta(2)-fumaronitrile)(PPh2Py)(2)] (4) which has been characterized by elemental analysis and NMR spectroscopy. Low temperature protonation of 4 with methanesulfonic acid leads to the bis-protonated species [Pd(eta(2)-fumaronitrile)(Ph2PPyH)(2)](CH3SO3)(2) (4a) which is stable only at temperatures < 0 degrees C. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.063
• 作为产物：
  描述：

  (2-methylallyl)palladium-chloride dimer 、 二苯基-2-吡啶膦 以 二氯甲烷 为溶剂， 以95%的产率得到{Pd(η3-methylallyl)(2-(diphenylphosphino)pyridine)Cl}
  参考文献：
  名称：

  Cationic palladium(II)-allyl-complexes containing 2-pyridyldiphenylphosphine: X-ray crystal structure of the binuclear complex [Pd(η3-2-Me-allyl)(μ-Ph2PPy)]2(BF4)2. Detection of an intramolecular C(allyl)–H⋯phenyl ring π-interaction

  摘要：

  Reaction of [PdCl(eta(3)-2-Me-allyl)(Ph2PPy)] (1) with AgBF4 affords the new dinuclear cationic complex [Pd(eta(3)-2-Me-allyl)(mu-Ph2PPy)](2)(BF4)(2) (2). The X-ray structural analysis of 2 shows that the 2-pyridyldiphenylphosphine ligands adopt a binucleating role through the P and N atoms bridging two independent palladium centres to form an eight-membered metallocyclic ring. One of the anti hydrogen atoms of the allyl moiety was located very close to a phenyl ring of Ph2PPY indicating the occurrence of a CH/pi interaction. Addition of one equivalent of Ph2PPy to complex (2) affords the mononuclear cationic complex [Pd(eta(3) -2-Me-allyl)(Ph2PPy)(2)](BF4) (3). (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.04.021

文献信息

• Steric effects of the 2-(diphenylphosphino)pyridine bridging ligand in the synthesis of binuclear palladium(II) complexes
  作者：Giovanni De Munno、Giuseppe Bruno、Carmela Grazia Arena、Dario Drommi、Felice Faraone

  DOI：10.1016/0022-328x(93)80165-8

  日期：1993.5

  with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] was crystallographically characterized: P21/n, a = 15.143(2), b

  用二氯甲烷中的顺式[Pd（t BuNC）2 Cl 2 ]处理[Pd CH 2 C（CH 3）CH 2 }（Ph 2 PPy）Cl]（Ph 2 PPy = 2-（二苯基膦基）吡啶），得到混合的异氰化物-叔膦配合物顺式[[Pd（t BuNC）Ph 2 PPy）Cl 2 ]，其中Ph 2 PPy是单齿P-给体，和[Pd [CH 2 C（CH 3）CH 2 ] Cl} 2 ]。Ph 2的空间位阻讨论了决定反应过程的PPy桥联配体。复杂的顺式- [钯（吨BuNC）（PH 2 PPY）氯2 ]的晶体学表征：P 2 1 / Ñ，一个= 15.143（2），b = 9.527（1），C ^ = 17.517（4）， β= 113.96（1）°，V = 2309.4（7）3，ž = 4.最后- [R值为0.044，[R瓦特= 0.046对于3078个反射与我>3σ（我）。
• Arena, Carmela Grazia; Rotondo, Enrico; Faraone, Felice, Organometallics, 1991, vol. 10, # 11, p. 3877 - 3885
  作者：Arena, Carmela Grazia、Rotondo, Enrico、Faraone, Felice、Lanfranchi, Maurizio、Tiripicchio, Antonio

  DOI：——

  日期：——