Dichloropalladium;[phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane | 1000592-05-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Dichloropalladium;[phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane
• CAS: 1000592-05-1
• 化学式: C₂₁H₂₀Cl₂NPPd
• 分子量: 494.696
• InChiKey: GUPPNAVFMMBBNR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.22
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 [Phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane 以 二氯甲烷 为溶剂， 以53%的产率得到Dichloropalladium;[phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane
  参考文献：
  名称：

  P,N-Chelate Complexes of Pd(II) and Pt(II) Based on a Phosphaalkene Motif:  A Catalyst for the Overman−Claisen Rearrangement

  摘要：

  The reaction of E/Z-MesP=C(Ph)(Py) (1, Mes = 2,4,6-Me(3)C(6)H(2)-) with (cod)PtCl(2) or (cod)PdCl(2) affords P,N-chelate complexes [MesP C(Ph)(Py)PtCl(2)] (2a) and [MesP=C(Ph)(Py)PdCl(2)] (2b), respectively. Compounds 2a and 2b were fully characterized spectroscopically, and both were characterized by X-ray crystallography. The molecular structures exhibited almost identical metrical parameters. The P=C bond lengths in 2a and 2b [1.672(4) and 1.675(3) A, respectively] were shortened substantially with respect to that of 1 [1.7043(16) A]. Complex 2b was explored as a catalyst for the Overman-Claisen rearrangement. Several allyl trichloroacetimidate substrates [HN=C(CCl(3))OCH(2)CH=CHR(1): 3a, R(1) = Me; 3b, R(1) = n-Pr; 3c, R(1) = n-Hep; 3d, R(1) = CH(2)CH(2)Ph; 3e, R(1) = i-Pr] were successfully rearranged to their respective branched amides [H(2)C=CHCH(R(1))NHC(O)CCl(3): 4a-e] using 5 mol % 2b as catalyst. Isolated yields ranged from a low of 33% for the bulky 4e to a high of 91% for 4a.

  DOI：

  10.1021/om700784x

文献信息

• P,N-Chelate Complexes of Pd(II) and Pt(II) Based on a Phosphaalkene Motif:  A Catalyst for the Overman−Claisen Rearrangement
  作者：Julien Dugal-Tessier、Gregory R. Dake、Derek P. Gates

  DOI：10.1021/om700784x

  日期：2007.12.1

  The reaction of E/Z-MesP=C(Ph)(Py) (1, Mes = 2,4,6-Me(3)C(6)H(2)-) with (cod)PtCl(2) or (cod)PdCl(2) affords P,N-chelate complexes [MesP C(Ph)(Py)PtCl(2)] (2a) and [MesP=C(Ph)(Py)PdCl(2)] (2b), respectively. Compounds 2a and 2b were fully characterized spectroscopically, and both were characterized by X-ray crystallography. The molecular structures exhibited almost identical metrical parameters. The P=C bond lengths in 2a and 2b [1.672(4) and 1.675(3) A, respectively] were shortened substantially with respect to that of 1 [1.7043(16) A]. Complex 2b was explored as a catalyst for the Overman-Claisen rearrangement. Several allyl trichloroacetimidate substrates [HN=C(CCl(3))OCH(2)CH=CHR(1): 3a, R(1) = Me; 3b, R(1) = n-Pr; 3c, R(1) = n-Hep; 3d, R(1) = CH(2)CH(2)Ph; 3e, R(1) = i-Pr] were successfully rearranged to their respective branched amides [H(2)C=CHCH(R(1))NHC(O)CCl(3): 4a-e] using 5 mol % 2b as catalyst. Isolated yields ranged from a low of 33% for the bulky 4e to a high of 91% for 4a.