cis-[PdCl2(CNC6H4OMe-p)2] | 40927-13-7

• 英文名称: cis-[PdCl2(CNC6H4OMe-p)2]
• 英文别名: cis-Cl2Pd(CNC64-p-OMe)2；Pd(CNC₆H₄-p-OMe)₂Cl₂；cis-[PdCl2(CN(4-MeOC6H4))2]
• CAS: 40927-13-7
• 化学式: C₁₆H₁₄Cl₂N₂O₂Pd
• 分子量: 443.625
• InChiKey: QFWQGWCFGCPQJY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  cis-[PdCl2(CNC6H4OMe-p)2] 、 甲基汞 在 P(C₆H₅)3 作用下， 以 苯 为溶剂， 以75%的产率得到trans-chloro-1,4-bis(p-methoxyphenyl)-1,4-diaza-3-methylbutadiene-2-yl-bis(triphenylphosphine)palladium(II)
  参考文献：
  名称：

  1,2-Bis(arylimino)propylpalladium complexes as N-donor chelate ligands towards metals of the first transition series

  摘要：

  DOI：

  10.1039/dt9780001478
• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 4-甲氧基苯异腈 以 二氯甲烷 为溶剂， 反应 0.17h， 以61%的产率得到cis-[PdCl2(CNC6H4OMe-p)2]
  参考文献：
  名称：

  Interplay of Metallophilic Interactions, π–π Stacking, and Ligand Substituent Effects in the Structures and Luminescence Properties of Neutral Pt^II and Pd^II Aryl Isocyanide Complexes

  摘要：

  Packing interactions in the crystal structures of a series of cis-M(CNAr)(2)Cl-2 complexes (M = Pt, Pd; Ar = substituted phenyl) were examined and correlated with the luminescence properties of the Pt complexes. The structures of the PhNC and p-tolyl isocyanide complexes exhibit extended chains of metallophilic interactions with M center dot center dot center dot M distances of 3.24-3.25 and 3.34 angstrom, respectively, with nearly isostructural Pt and Pd compounds. Both structure types contain void channels running parallel to the M center dot center dot center dot M chains. The channels are 3-4 angstrom wide and vacant for the phenyl structures, while those in the p-tolyl structures are up to 7.6 angstrom wide and contain water. These channeled structures are stabilized by a combination of metallophilic bonding and aryl pi-pi stacking interactions. The Pt structure with 4-F substituents also features extended Pt center dot center dot center dot Pt chains, but with longer 3.79 angstrom distances alternating with shorter 3.37 angstrom contacts. Structures with 4-CF3 and 4-OMe substituents exhibit mostly isolated dimers of M center dot center dot center dot M contacts. In complexes with 2,6-dimethylphenyl isocyanide, steric hindrance precludes any short M center dot center dot center dot M contacts. The primary effect of aryl substitution is to provide alternative packing motifs, such as CF3 center dot center dot center dot pi and CH3 center dot center dot center dot pi interactions, that either augment or disrupt the combination of metallophilic contacts and pi-pi stacking needed to stabilize extended M center dot center dot center dot M chains. Differences in the Pt and Pd structures containing 4-F and 4-OMe substituents are consistent with a higher driving force for metallophilic interactions for Pt versus Pd. The M-C and M-Cl bond distances indicate a slightly higher trans influence for aryl isocyanides bound to Pt versus Pd. The three extended Pt center dot center dot center dot Pt chain structures display luminescence assignable to (d sigma*-p sigma) excited states, demonstrating the existence of substantial orbital communication along the metal-metal chains. Face-indexing shows that the preferred crystal growth axis is along the metal-metal chains for the luminescent structures. Variable temperature structural studies showed that both M center dot center dot center dot M and pi-pi interactions contract upon cooling. Overall, this study suggests that synergy with pi-pi and other interactions is necessary to stabilize extended M center dot center dot center dot M chain structures. Thus, efforts to design functional materials based on metallophilic bonding must consider the full array of available packing motifs.

  DOI：

  10.1021/ic301104a

文献信息

• Reactions of palladium(<scp>II</scp>) allyl dimers with palladium(<scp>II</scp>) complexes containing σ-bonded 1,2-bis(imino)alkyl groups. Crystal and molecular structure of the zwitterionic binuclear compound [Pd(η³-2-MeC₃H₄){R¹NC(PdCl₂L)–CMeNR²}](L = PPh₃, R¹= R²= C₆H₄OMe-p)
  作者：Bruno Crociani、Roberta Bertani、Tristano Boschi、Giuliano Bandoli

  DOI：10.1039/dt9820001715

  日期：——

  2-bis(imino)alkylpalladium derivatives (A), R1NCL′–CR3NR2[R1= R2= C6H4OMe-p, R3= Me, L′=trans-PdCIL2(L =para-substituted triarylphosphine or AsPh3); R1= R2= C6H4OMe-p, R3= H or Ph, L′=trans-PdCl(PPh3)2; R1= C6H4OMe-p, R2= R3= Me, L′=trans-PdCl(PPh3)2] react with [PdCl(η3-2-R4C3H4)}2](R4= H or Me) in the presence of NaClO4 to yield the cationic binuclear complexes (B), [Pd(η3-2-R4C3H4)(R1NCL′–CR3NR2)][ClO4]

  1,2-双（亚氨基）烷基钯衍生物（A），R 1 N CL'–CR 3 NR 2 [R 1 = R 2 = C 6 H 4 OMe- p，R 3 = Me，L'=反式- PdCIL 2（L =对位取代的三芳基膦或AsPh 3）；R 1＝ R 2＝ C 6 H 4 OMe- p，R 3＝ H或Ph，L′＝反式-PdCl（PPh 3）2；R 1 = C 6ħ 4 OMe- p，R 2 = R 3 = Me中，L'=反式-PdCl（PPH 3）2 ]与[的PdCl（η 3 -2-R 4 Ç 3 ħ 4）} 2 ]（R 4 =以次氯酸钠的存在下H或Me）4，得到阳离子双核配合物（B），[将Pd（η 3 -2-R 4 ç 3 ħ 4）（R 1 ñ CL'-CR 3 NR 2）] [ ClO 4 ]，其中1,2。双（亚氨基）烷基充当σσ'-NN '螯合配体。在不存在的NaClO的4，将反应引线最初的离子化合物的形成（C），[将Pd（η
• Bertani, Roberta; Mozzon, Mirto; Michelin, Rino A., Inorganic Chemistry, 1988, vol. 27, # 16, p. 2809 - 2815
  作者：Bertani, Roberta、Mozzon, Mirto、Michelin, Rino A.

  DOI：——

  日期：——
• Bertani, Roberta; Mozzon, Mirto; Benetollo, Franco, Journal of the Chemical Society, Dalton Transactions
  作者：Bertani, Roberta、Mozzon, Mirto、Benetollo, Franco、Bombieri, Gabriella、Michelin, Rino A.

  DOI：——

  日期：——
• Novel Metal-Mediated (M = Pd, Pt) Coupling between Isonitriles and Benzophenone Hydrazone as a Route to Aminocarbene Complexes Exhibiting High Catalytic Activity (M = Pd) in the Suzuki−Miyaura Reaction
  作者：Konstantin V. Luzyanin、Alexander G. Tskhovrebov、M. Carolina Carias、M. Fátima C. Guedes da Silva、Armando J. L. Pombeiro、Vadim Yu. Kukushkin

  DOI：10.1021/om900682v

  日期：2009.11.23

  Metal-mediated reaction between equimolar amounts of cis-[MCl2(C NR)(2)] [M = Pd, R = cyclohexyl (Cy) 1, tBu 2, 2,6-Me2C6H3 (Xyl) 3, 4-MeOC6H4 4; M = Pt, R = cyclohexyl (Cy) 5, 2,6-Me2C6H3 (Xyl) 7,4-MeOC6H4 8] and benzophenone hydrazone, H2N-N=CPh2, proceeds in CHCl3 under reflux for 8 h. The subsequent workup, provides the carbene species cis-[MCl2C(N(H)N=CPh2)=N(H)R}(C NR)] (M = Pd, 9-12; M = Pt, 13-15) in good (80-85%) isolated yields. Complexes 9-15 are air- and moisture-stable in the 20-80 degrees C temperature range and were characterized by elemental analyses (C, H, N), ESI+-MS, IR, and ID (H-1,C-13H-1}) and 2D (H-1,H-1-COSY, H-1,C-13-HMQC/H-1,C-13-HSQC, H-1,C-13-HMBC) NMR spectroscopies. In addition, the structures of two metallacarbenes, 11 and 14, were elucidated by single-crystal X-ray diffraction. The catalytic properties of 9-15 in the Suzuki-Miyaura cross-coupling of the aryl bromides 4-(RC6H4Br)-C-2 (R-2 = H, Me, OMe, and NO2) with phenylboronic acid (in EtOH as a solvent, K2CO3 as a base, 80 degrees C), yielding biaryl species, were evaluated, and it was found that the palladium-aminocarbene species 9-12 exhibit a high catalytic activity (yields up to 97%, TONS up to 1.4 x 10(6)).