cis-(1-phenyl-3,4-dimethylphosphole)2PdCl2 | 66368-11-4

• 英文名称: cis-(1-phenyl-3,4-dimethylphosphole)2PdCl2
• 英文别名: cis-(1-phenyl-3,4-dimethylphosphole)2PdCl2 C24H26Cl2P2Pd, yellow, monoclinic, P21/C
• CAS: 66368-11-4；72937-30-5；73244-96-9
• 化学式: C₂₄H₂₆Cl₂P₂Pd
• 分子量: 553.744
• InChiKey: CEDBTYQSMZKDKI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.61
• 重原子数：
  29.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  cis-(1-phenyl-3,4-dimethylphosphole)2PdCl2 以 neat (no solvent) 为溶剂， 生成 、 、
  参考文献：
  名称：

  Thermal Coupling Reactions of 1-Phenyl-3,4-dimethylphosphole within the Coordination Sphere of Palladium(II)

  摘要：

  The thermolyses of dihalobis(1-phenyl-3,4-dimethylphosphole)palladium(II) complexes [(DMPP)(2)PdX(2), X = Cl, Br, I] were investigated in 1,1,2,2-tetrachloroethane solutions at 145 degrees C and in the crystalline state at 140 OC. For cis-(DMPP)(2) PdCl2 and cis- or trans-(DMPP)(2) PdBr2 four types of products were formed: (1) [4 + 2] cycloaddition products, (2) [2 + 2] cycloaddition products, (3) compounds that result from 1,5-hydrogen migration from a methyl group on one phosphole to the beta-carbon of an adjacent phosphole (exo-methylene), and (4) products that result from an intermolecular [4 + 2] coupling of two phospholes followed sequentially by phosphinidene elimination and intramolecular [4 + 2] cycloaddition to another phosphole to give diphosphatetracyclotetradecatrienes (DPTCT). trans-(DMPP)(2)PdBr2 undergoes thermal isomerization to cis-(DMPP)(2)PdBr2 in the solid state, and cis- and trans-(DMPP)2PdBr2 give the same products in both their solid- and solution-slate thermolyses. In contrast, trans-(DMPP)(2) PdI2 neither isomerizes to the cis-isomer nor undergoes any of the phosphole coupling reactions in either the solution or solid state. The crystal structures of trans-(DMPP)(2)PdX(2) (X = Br, I), {(DMPP)(2)[2 + 2]}PdBr2, {(DMPP)(2)(exo-methylene)}PdBr2, and (DPTCT)PdCL(2) were determined. They crystallize in the monoclinic P2(1)/c, triclinic P (1) over bar, monoclinic P2(1)/c, monoclinic P2(1)/n, and orthorhombic P2(1)2(1)2(1) space groups in units cells of the following dimensions: a 10.158 (3) Angstrom, b = 14.876 (4) Angstrom, 16.829 (5) Angstrom, beta = 104.25 (2)degrees, rho(calc) 1.732 g/cm(3), Z = 4; a = 9.025(1) Angstrom, b = 11.023 (1) Angstrom, c 13.833 (1) Angstrom, alpha = 101.15 (1)degrees, beta = 98.82 (1)degrees, gamma = 105.30 (1)degrees, rho(calc) = 1,886 g/cm(3), Z = 2; a = 13.090 (2) Angstrom, b = 17.637 (2) Angstrom, c = 21.834 (2) Angstrom, beta = 100.51 (1)degrees, rho(calc) = 1.738 g/cm(3), Z = 4, a = 10.721 (1) Angstrom, b = 16.929 (1) Angstrom, c = 14.675(1) Angstrom, beta = 97.86 (1)degrees, rho(calc) = 1.663 g/cm(3), Z = 4; and a = 15.532 (3) Angstrom, b = 19.401 (4) Angstrom, c = 9.910 (2) Angstrom, rho(calc) = 1.490 g/cm(3), Z = 2, respectively. Least-squares refinements converged at final values of R(F) of 0.041, 0.0354, 0.0624, 0.0533, and 0.035 for 2770, 2672, 2729, 2159, and 2525 independent observed reflections, respectively. Kinetic studies suggest that the reaction mechanisms are the same in both the solid and solution states and that the reaction mechanisms are substantially different from those previously reported for the thermolyses of the analogous cis-(DMPP)(2)PtX(2) complexes.

  DOI：

  10.1021/ic951307f
• 作为产物：
  描述：

  1-苯基-3,4-二甲基膦杂环戊二烯) 、 sodium chloride 、 palladium dichloride 以 二氯甲烷 、 水 为溶剂， 以95.7%的产率得到cis-(1-phenyl-3,4-dimethylphosphole)2PdCl2
  参考文献：
  名称：

  Thermal Coupling Reactions of 1-Phenyl-3,4-dimethylphosphole within the Coordination Sphere of Palladium(II)

  摘要：

  The thermolyses of dihalobis(1-phenyl-3,4-dimethylphosphole)palladium(II) complexes [(DMPP)(2)PdX(2), X = Cl, Br, I] were investigated in 1,1,2,2-tetrachloroethane solutions at 145 degrees C and in the crystalline state at 140 OC. For cis-(DMPP)(2) PdCl2 and cis- or trans-(DMPP)(2) PdBr2 four types of products were formed: (1) [4 + 2] cycloaddition products, (2) [2 + 2] cycloaddition products, (3) compounds that result from 1,5-hydrogen migration from a methyl group on one phosphole to the beta-carbon of an adjacent phosphole (exo-methylene), and (4) products that result from an intermolecular [4 + 2] coupling of two phospholes followed sequentially by phosphinidene elimination and intramolecular [4 + 2] cycloaddition to another phosphole to give diphosphatetracyclotetradecatrienes (DPTCT). trans-(DMPP)(2)PdBr2 undergoes thermal isomerization to cis-(DMPP)(2)PdBr2 in the solid state, and cis- and trans-(DMPP)2PdBr2 give the same products in both their solid- and solution-slate thermolyses. In contrast, trans-(DMPP)(2) PdI2 neither isomerizes to the cis-isomer nor undergoes any of the phosphole coupling reactions in either the solution or solid state. The crystal structures of trans-(DMPP)(2)PdX(2) (X = Br, I), {(DMPP)(2)[2 + 2]}PdBr2, {(DMPP)(2)(exo-methylene)}PdBr2, and (DPTCT)PdCL(2) were determined. They crystallize in the monoclinic P2(1)/c, triclinic P (1) over bar, monoclinic P2(1)/c, monoclinic P2(1)/n, and orthorhombic P2(1)2(1)2(1) space groups in units cells of the following dimensions: a 10.158 (3) Angstrom, b = 14.876 (4) Angstrom, 16.829 (5) Angstrom, beta = 104.25 (2)degrees, rho(calc) 1.732 g/cm(3), Z = 4; a = 9.025(1) Angstrom, b = 11.023 (1) Angstrom, c 13.833 (1) Angstrom, alpha = 101.15 (1)degrees, beta = 98.82 (1)degrees, gamma = 105.30 (1)degrees, rho(calc) = 1,886 g/cm(3), Z = 2; a = 13.090 (2) Angstrom, b = 17.637 (2) Angstrom, c = 21.834 (2) Angstrom, beta = 100.51 (1)degrees, rho(calc) = 1.738 g/cm(3), Z = 4, a = 10.721 (1) Angstrom, b = 16.929 (1) Angstrom, c = 14.675(1) Angstrom, beta = 97.86 (1)degrees, rho(calc) = 1.663 g/cm(3), Z = 4; and a = 15.532 (3) Angstrom, b = 19.401 (4) Angstrom, c = 9.910 (2) Angstrom, rho(calc) = 1.490 g/cm(3), Z = 2, respectively. Least-squares refinements converged at final values of R(F) of 0.041, 0.0354, 0.0624, 0.0533, and 0.035 for 2770, 2672, 2729, 2159, and 2525 independent observed reflections, respectively. Kinetic studies suggest that the reaction mechanisms are the same in both the solid and solution states and that the reaction mechanisms are substantially different from those previously reported for the thermolyses of the analogous cis-(DMPP)(2)PtX(2) complexes.

  DOI：

  10.1021/ic951307f

文献信息

• Cooperative Diastereoselectivity of Palladium- and Platinum-Promoted Intramolecular [4+2] Diels−Alder Cycloaddition Reactions of 3,4-Dimethyl-1-phenylphosphole
  作者：Kent D. Redwine、William L. Wilson、Donald G. Moses、Vincent J. Catalano、John H. Nelson

  DOI：10.1021/ic990885j

  日期：2000.7.24

  with 2 equiv of the dienophiles N,N-dimethylacrylamide (DMAA), 2-vinylpyridine (VyPy), and diphenylvinylphosphine (DPVP) to form bis-[4 + 2] Diels-Alder cycloaddition products. The [M(DMPP)2(DMAA)2]2+ and [M(DMPP)2(VyPy)2]2+ complexes form exclusively as the cis-geometric isomers, whereas for [M(DMPP)2(DPVP)2]2+, both cis- and trans-geometric isomers are formed. The two Diels-Alder cycloadditions occur

  配合物[（DMPP）2M（CH3CN2）] X2（DMPP = 3,4-二甲基-1-苯基磷; M = Pd，Pt; X = BF4-，NO3-，ClO4-）与2当量的亲二烯体N反应，N-二甲基丙烯酰胺（DMAA），2-乙烯基吡啶（VyPy）和二苯基乙烯基膦（DPVP）形成双-[4 + 2] Diels-Alder环加成产物。[M（DMPP）2（DMAA）2] 2+和[M（DMPP）2（VyPy）2] 2+络合物仅形成为顺式几何异构体，而对于[M（DMPP）2（DPVP）2 ] 2+，同时形成顺式和反式异构体。两个Diels-Alder环加成顺序发生，并且第一个反应的绝对构型影响第二个反应的绝对构型。在所有情况下，都会形成（R，R）和（S，S）非对映异构体的残留混合物。没有观察到内消旋（R，S）非对映异构体。新的配合物的特征在于元素分析，物理性质，
• Redistribution reactions of platinum(II) and palladium(II) phosphine complexes
  作者：Jeffrey A. Rahn、Mark S. Holt、John H. Nelson

  DOI：10.1016/s0277-5387(00)86441-4

  日期：1989.1

  Abstract Anion redistribution equilibria of the type (R 3 P) 2 MX 2 + (R 3 P) 2 MY 2 ⇆ 2(R 3 P) 2 MXY (X, Y = Cl, Br, I, CN, N 3 ; R 3 P = Me 2 PhP, MePh 2 P, (Bzl) 3 P, (CH 2 CH) 2 PhP, (CH 2 CH)Ph 2 P and 1-phenyl-3,4-dimethylphosphole; M = Pd, Pt) have been studied by 31 P 1 H} and in some cases 195 Pt 1 H} NMR spectroscopy. It was found that except for the two cases when R 3 P = MePh 2 P, M

  摘要（R 3 P）2 MX 2 +（R 3 P）2 MY 2⇆2（R 3 P）2 MXY（X，Y = Cl，Br，I，CN，N 3; R 3 P = Me 2 PhP，MePh 2 P，（Bzl）3 P，（CH 2 = CH）2 PhP，（CH 2 = CH）Ph 2 P和1-苯基-3,4-二甲基磷脂; M = Pd， Pt）已通过31 P 1 H}和某些情况下的195 Pt 1 H} NMR光谱进行了研究。发现除了两种情况，当R 3 P = MePh 2 P，M = Pd，X = Cl，Y = Br和R 3 P = Me 2 PhP，M = Pd，X = Cl，Y = Br时，重新分配通常是瞬时的。（R 3 P）2 PdCl 2 +（R 3 P）2 Pd（CN）2反应较慢，但已完成。相反，当一个阴离子为CN-时，即使一个月后，铂络合物也未观察到阴离子再分布。混合阴离子物质相对于对称物
• Metal-template synthesis and co-ordination properties of a palladium complex containing a novel and stable imidazole-substituted phosphine C–P bidentate chelate
  作者：Huifang Lang、Jagadese J. Vittal、Pak-Hing Leung

  DOI：10.1039/a803820a

  日期：——

  An organopalladium complex promoted Diels–Alder reaction between 1-phenyl-3,4-dimethylphosphole and 1-vinylimidazole gave a novel imidazole-substituted phosphanorbornene bidentate ligand which co-ordinated to the palladium template via the C2 carbon atom of the imidazole group and the bridgehead phosphorus donor atom.

  有机钯络合物促进了 1-苯基-3,4-二甲基膦和 1-乙烯基咪唑之间的 DielsâAlder 反应，产生了一种新型咪唑取代的磷降冰片烯双齿配体，该配体通过咪唑基团的 C2 碳原子和桥头磷供体原子与钯模板配位。
• Rahn, Jeffrey A.; Holt, Mark S.; Gray, George A., Inorganic Chemistry, 1989, vol. 28, # 2, p. 217 - 226
  作者：Rahn, Jeffrey A.、Holt, Mark S.、Gray, George A.、Alcock, Nathaniel W.、Nelson, John H.

  DOI：——

  日期：——
• Phospholes as ligands: palladium(II) complexes of 1-substituted 3,4-dimethylphospholes. Structure and properties
  作者：J. Jeffrey MacDougall、John H. Nelson、Francois Mathey、James J. Mayerle

  DOI：10.1021/ic50205a026

  日期：1980.3