trans-[PdCl₂(EtCN)₂] | 27928-79-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-[PdCl₂(EtCN)₂]
• 英文别名: trans-[PdCl2(C2H5CN)2]；palladium(2+);propanenitrile;dichloride
• CAS: 27928-79-6；26047-46-1
• 化学式: C₆H₁₀Cl₂N₂Pd
• 分子量: 287.485
• InChiKey: NOAKEPLADHCTBH-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-[PdCl₂(EtCN)₂] 、 N-(diphenylmethylene)-4-methylaniline oxide 反应 4.0h， 以90%的产率得到[PdCl₂{N=C(Et)ON(C₆H₄Me-p)CPh₂}₂]
  参考文献：
  名称：

  A Palladium(II) Center Activates Nitrile Ligands toward 1,3-Dipolar Cycloaddition of Nitrones Substantially More than the Corresponding Platinum(II) Center

  摘要：

  Palladium(II)-coordinated NCR1 (R-1 = Et (1), NMe2 (2), Ph (3)) species react smoothly with acyclic nitrones such as the ketonitrones Ph2C=N(O)R-4 (R-4 = p-MeC6H4 (4), p-ClC6H4 (5)) and the aldonitrone p-MeC6H4CH=N(O)Me (6) in the corresponding nitrile media. This reaction proceeds as a consecutive two-step intermolecular cycloaddition to give the mono- and bis-2,3-dihydro-1,2,4-oxadiazole complexes [PdCl2((RCN)-C-1){N-a=C (R-1) ON (R-4)C-b((RR3)-R-2)}}((a-b)) (7a-13a; R-2, R-3 = Ph; R-4 = C6H4Me-p, R-1 = Et (7), NMe2 (8), Ph (9); R4 = C6H4C1-p, = Et (10), NMe2 (11), Ph (12); R2 = H, R-3 = C6H4Me-p, R-4 = Me, R-1 = NMe2 (13)) and [PdCl2{Na= C(R-1)ON(R-4)Cb((RR3)-R-2)}(2)]((a-b)) (7b-13b), respectively. Inspection of the obtained data and their comparison with the previous results indicate that the Pd-II centers provide substantially greater activation of RCN ligands toward the 1,3-dipolar cycloaddition than the relevant Pt-II centers. The palladium(II)-mediated 1,3-dipolar cycloaddition of ketonitrones to nitriles is reversible. All complexes were characterized by elemental analyses (C, H, N), high-resolution ESI-MS, and IR and H-1 and C-13{H-1} NMR spectroscopy. The structure of trans7b was determined by single-crystal X-ray diffraction. Metal-free 5-NR'2-2,3-dihydro-1,2,4-oxadiazoles (7c-13c) were liberated from the corresponding (2,3-dihydro-1,2,4-oxadiazole)2Pd(II) complexes by treatment with 1,2-(diphenylphosphino)ethane, and the heterocycles were characterized by high-resolution ESI+-MS and H-1 and 13C{IFI} spectroscopy.

  DOI：

  10.1021/ic301866y

文献信息

• Synthesis of (1,2,4‐Oxadiazole)palladium( <scp>II</scp> ) Complexes by [2 + 3] Cycloaddition of Nitrile Oxides to Organonitriles in the Presence of PdCl ₂
  作者：Nadezhda A. Bokach、Vadim Yu. Kukushkin、Matti Haukka、Armando J. L. Pombeiro

  DOI：10.1002/ejic.200400580

  日期：2005.3

  the nitrile oxides 2,4,6-R' 3 C 6 H 2 CNO (R' = Me, OMe) and trans-[PdCl 2 (RCN) 2 ], or RCN (R = Me, Et, CH 2 CN, NMe 2 , Ph) in the presence of PdCl 2 , proceeded smoothly under mild conditions and allowed the isolation of the 1,2,4-oxadiazole complexes trans-[PdCl 2 (N a =C(R)-ON=C b (C 6 H 2 R' 3 )(N a -C b )} 2 ] (1-8) in 40-85% yields. In CH 2 Cl 2 , the reaction between 2,4,6-R' 3 C 6 H 2 CNO

  通过与1,2-双（二苯基膦基）乙烷或过量的Na 2 S.7H 2 O在MeOH中的取代反应，成功地从1-8中释放杂环物质；释放的 1,2,4-恶二唑 (11-18) 通过正离子 FAB 质谱和 1 H 和 1 3 C 1 H} NMR 光谱表征。
• A Palladium(II) Center Activates Nitrile Ligands toward 1,3-Dipolar Cycloaddition of Nitrones Substantially More than the Corresponding Platinum(II) Center
  作者：Andreii S. Kritchenkov、Nadezhda A. Bokach、Galina L. Starova、Vadim Yu. Kukushkin

  DOI：10.1021/ic301866y

  日期：2012.11.5

  Palladium(II)-coordinated NCR1 (R-1 = Et (1), NMe2 (2), Ph (3)) species react smoothly with acyclic nitrones such as the ketonitrones Ph2C=N(O)R-4 (R-4 = p-MeC6H4 (4), p-ClC6H4 (5)) and the aldonitrone p-MeC6H4CH=N(O)Me (6) in the corresponding nitrile media. This reaction proceeds as a consecutive two-step intermolecular cycloaddition to give the mono- and bis-2,3-dihydro-1,2,4-oxadiazole complexes [PdCl2((RCN)-C-1)N-a=C (R-1) ON (R-4)C-b((RR3)-R-2)}}((a-b)) (7a-13a; R-2, R-3 = Ph; R-4 = C6H4Me-p, R-1 = Et (7), NMe2 (8), Ph (9); R4 = C6H4C1-p, = Et (10), NMe2 (11), Ph (12); R2 = H, R-3 = C6H4Me-p, R-4 = Me, R-1 = NMe2 (13)) and [PdCl2Na= C(R-1)ON(R-4)Cb((RR3)-R-2)}(2)]((a-b)) (7b-13b), respectively. Inspection of the obtained data and their comparison with the previous results indicate that the Pd-II centers provide substantially greater activation of RCN ligands toward the 1,3-dipolar cycloaddition than the relevant Pt-II centers. The palladium(II)-mediated 1,3-dipolar cycloaddition of ketonitrones to nitriles is reversible. All complexes were characterized by elemental analyses (C, H, N), high-resolution ESI-MS, and IR and H-1 and C-13H-1} NMR spectroscopy. The structure of trans7b was determined by single-crystal X-ray diffraction. Metal-free 5-NR'2-2,3-dihydro-1,2,4-oxadiazoles (7c-13c) were liberated from the corresponding (2,3-dihydro-1,2,4-oxadiazole)2Pd(II) complexes by treatment with 1,2-(diphenylphosphino)ethane, and the heterocycles were characterized by high-resolution ESI+-MS and H-1 and 13CIFI} spectroscopy.