Pd(2-(dimethylaminomethyl)phenyl-C(1),N)(acetylacetonate) | 39046-23-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: Pd(2-(dimethylaminomethyl)phenyl-C(1),N)(acetylacetonate)
• 英文别名: Pd(N,N-dimethylbenzylamine-C(2),N)(acetylecetonate-O,O')；(2-[(dimethylamino-κN)methyl]phenyl-κC¹)Pd(acac)；(N,N-dimethylbenzylamine(-1H)-κ2N,C)Pd(acetylacetonate)
• CAS: 39046-23-6
• 化学式: C₁₄H₁₉NO₂Pd
• 分子量: 339.73
• InChiKey: DCKGAJOLPOVHKT-UHFFFAOYSA-N

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：

  Pd(2-(dimethylaminomethyl)phenyl-C(1),N)(acetylacetonate) 、 N-乙酰甘氨酸 以 甲醇 为溶剂， 反应 0.5h， 以71%的产率得到
  参考文献：
  名称：

  单N保护的氨基酸配体可稳定二聚钯（II）配合物对CH功能化的重要性

  摘要：

  单保护的氨基酸（MPAA）配体用于许多Pd催化的CH官能化反应中。已经提出了MPAA经由2-（N，O）配位结合至Pd（II），但是这种结合尚未在实验上得到验证。本文中，我们报告了在MPAAs存在下，通过对二甲基苄胺进行环palpalpalation制备的一系列MPAA复合物的合成和详细表征。分离的复合物以μ-羧基（MPAA）桥接的二聚体形式存在，并且具有潜在的MM协同作用和二级球氢键键合的特征。都可以观察到选择性的MP AA配位和立体化学的传递，以前都认为是由2-（N，O）MPAA配位产生的。当用用于催化CH官能化的亲电试剂处理时，分离出的MPAA复合物会形成CC和CX（X = Cl，Br，I）键。发现MPAA palladacycles的化学计量碘化是通过双核钯物质与一当量的碘进行的，分离出的配合物也可作为催化CH功能化的可行前催化剂。总之，这些结果为与CH键功能化相关的Pd-MPAA复合物的反应性提供了许多见解。

  DOI：

  10.1039/c7sc01674c
• 作为产物：
  描述：

  二-μ-氯双[2-[(二甲氨基)甲基]苯基-C,N]二钯(Ⅱ) 、 thallium(I) 2,4-pentanedionate 以 二氯甲烷 为溶剂， 以92%的产率得到Pd(2-(dimethylaminomethyl)phenyl-C(1),N)(acetylacetonate)
  参考文献：
  名称：

  Metal complexes of biologically important ligands: Synthesis of amino acidato complexes of PdII containing a C,N-cyclometallated group as an ancillary ligand

  摘要：

  New amino acidato complexes of Pd-II of stoichiometry [Pd(C-N)(Aa)](C-N = C,N-cyclometallated ligand, Aa = N,O-amino acidato ligand) have been obtained by reaction of [Pd(C-N)(acac)] (C-N = N,N-dimethylbenzylamine-C-2,N (dmba) (1) or N,N-dimethyl(S-alpha-phenylethyl)amine-C-2,N (S-dmphea) (2)) with glycine, chiral amino acids (alanine, phenylalanine and valine), and amino acid derivatives (N-acetylglycine and N-acetyl-alpha,beta-dehydroalanine) in MeOH. The compounds are characterized by IR, H-1 and C-13 NMR. The geometry of these complexes has been unambiguously determined by NOE difference experiments and NOESY measurements.

  DOI：

  10.1016/0022-328x(94)05204-o

文献信息

• Synthesis and structural characterisation of 1’-(diphenylphosphino)ferrocene-1-phosphonic acid, its ammonium salts and Pd(II) complexes
  作者：Filip Horký、Ivana Císařová、Jiří Schulz、Petr Štěpnička

  DOI：10.1016/j.jorganchem.2019.04.012

  日期：2019.8

  ligands, [(LCY)Pd(acac)] (LCY = 2-[(dimethylamino-κN)methyl]phenyl-κC1 and 2-[(methylthio-κS)methyl]phenyl-κC1), H2L gave rise to bis-chelate complexes of the [(LCY)Pd(HL-κ2O,P)] type. H2L, the ammonium salts featuring the HL− anion, and all Pd(II) complexes were structurally characterised by single-crystal X-ray diffraction analysis. Variations in phosphonate P-O bond lengths observed in the crystal

  一种新的极性膦基二茂铁配体，即。通过水解相应的膦酸酯乙酯制备1'-（二苯基膦基）二茂铁-1-膦酸（H 2 L）。但是，该化合物相对不稳定，经长时间保存后会逐渐分解，最终得到氧化膦H 2 LO。当膦部分受到保护时（例如，在氧化膦H 2 L O和加合物H 2 L ·BH 3中），没有观察到分解。一种替代方法，以制备更稳定的ħ 2大号由膦酸转化为铵盐（dabcoH）（H代理人大号）和[（OHCH2 CH 2）2 NH 2 ]（H L）（dabco = 1,4-二氮杂双环[2.2.2]辛烷）没有明显的稳定作用。ħ 2大号与[的PdCl 2（COD）]（COD =环辛-1,5-二烯），制造双（膦）复合物，反式- [的PdCl 2（H 2大号-κ P）2 ]。当用Pd（II）-acetylacetonate（ACAC）配合物混合邻-metallated辅助配体，[（L CY）的Pd（aCAC）]的（L
• Synthesis and characterization of dinuclear complexes of PdII containing the (μ-NCS)2 skeleton
  作者：Maria Espino Lizarraga、Rafael Navarro、Esteban P. Urriolabeitia

  DOI：10.1016/s0022-328x(97)00316-1

  日期：1997.9

  eliminated as acetylacetone, and N,S-bridging coordination of the anionic groups [N ∧ S]−, giving the corresponding neutral dinuclear derivatives [Pd(C ∧ N)(μ-N ∧ S)]2 (C ∧ N = dmba, N ∧ S = pyS 1, bztzS 2, pymS 3, bzmdS 4, tzS 5; C ∧ N = 8-mq, N ∧ S = pyS 6, bztzS 7, pymS 8, bzmdS 9, tzS 10). In these complexes, two [Pd(C ∧ N)]+ fragments are bridged by two [N ∧ S]− ligands in a head-to-tail disposition

  [Pd（C ＝ N）acac）] [C ＝ N ＝ dmba（2-（二甲基氨基甲基）苯基-C 1，N），8-mq（8-喹啉基甲基-C，N）的反应。acac =乙酰丙酮酸酯]与2巯基衍生物H [N S] H [N S] = pySH（2-巯基吡啶），bztzSH（2-巯基苯并噻唑），pymSH（2-巯基嘧啶），bzmdSH（2-巯基苯并咪唑） ）和tzSH（2-巯基噻唑啉）}以1：1的摩尔比（CH 2 Cl 2，室温）导致乙酰丙酮配体的质子化，该乙酰丙酮配体作为乙酰丙酮被消除，并且N，S桥连阴离子组[N∧S] -，给出相应的中性双核衍生物[Pd（C N）（μ- N S）] 2（C N N = dmba，N S = pyS 1，bztzS 2，pymS 3，bzmdS 4，tzS 5； C N ＝ 8-mq，NS ＝ pyS 6，bztzS 7，pymS 8，bzmdS 9，tzS 10）。在这些配合物中，两个[Pd（C∧N）]
• Synthesis of Two Isomeric Ferrocene Phosphanylcarboxylic Acids and their Pd ^II Complexes with and without Auxiliary <i>ortho</i> ‐Metalated C,E‐Ligands (E = N and S)
  作者：Martin Zábranský、Ivana Císařová、Petr Štěpnička

  DOI：10.1002/ejic.201700167

  日期：2017.5.18

  Two homologous ferrocene phosphanylcarboxylic acids, viz., 1′-[(diphenylphosphanyl)methyl]ferrocene-1-carboxylic acid (HL1) and [1′-(diphenylphosphanyl)ferrocenyl]acetic acid (HL2), were synthesized and studied as ligands in PdII complexes. The addition of these hybrid donors to [PdCl2(MeCN)2] led to the bis-phosphane complexes trans-[PdCl2(HL1-κP)2] and trans-[PdCl2(HL2-κP)2]. In contrast, the reactions

  合成并研究了两种同源的二茂铁膦基羧酸，即1'-[（（二苯基膦基）甲基]二茂铁-1-羧酸（HL 1）和[1'-（二苯基膦基）二茂铁基]乙酸（HL 2）。 Pd II复合物中的配体。加入这些杂交捐助[的PdCl的2（MeCN中）2 ]导致双-膦配合物的反式- [的PdCl 2（HL 1 -κ P）2 ]和反式- [的PdCl 2（HL 2 -κ P）2]。相比之下，反应HL 1和HL 2与钯II乙酰丙酮（ACAC）络合物[（L YC）的Pd（aCAC）]的，其中L YC = 2 - [（二甲基氨基- κ Ñ）甲基]苯基κ Ç 1（L NC）和2 - [（甲硫基κ小号）甲基]苯基-κ ç 1（L SC），质子转移和更换ACAC配体下进行，从而产生O，P-桥接phosphanylcarboxylate二聚体[L YC Pd（µ（P，O）-L 1）] 2和分子螯合物[L YC Pd（大号2 -κ 2
• Synthesis of a Polar Phosphinoferrocene Amidosulfonate Ligand and Its Application in Pd-Catalyzed Cross-Coupling Reactions of Aromatic Boronic Acids and Acyl Chlorides in an Aqueous Medium
  作者：Karel Škoch、Ivana Císařová、Petr Štěpnička

  DOI：10.1021/acs.organomet.6b00600

  日期：2016.10.10

  The reaction of [1'-(diphenylphosphino)ferrocenyl]methylamine (1), generated in situ from its hydrochloride and triethylamine, with 2-sulfobenzoic anhydride afforded an anionic phosphino-amide, which was isolated as a triethylammonium salt, Ph(2)PfcCH(2)NHCOC(6)H(4)SO(3)-(HNEt3) (2; fc = ferrocene-1,1'-diyl). A similar reaction of 1 with phthalic anhydride only furnished the salt (Ph(2)PfcCH(2)NH(3))[C6H4CO2H(CO2)]. When it was reacted with [PdCl2(MeCN)(2)] and [(LPd)-Pd-NC(mu-Cl)](2) (L-NC = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1), compound 2 gave rise to the bisphosphine complex [PdCl2(2-kappa P)(2)] and the bridge-cleavage product [(LPdCl)-Pd-NC(2-kappa P)], respectively. An analogue of the latter complex containing 2'-amino-[1,1'-biphenyl]-2-yl-kappa N-2,C-2 as the auxiliary chelating ligand, compound 8, was prepared in a similar manner from 2 and the respective Pd precursor. Finally, the reaction of 2 with [(LPd)-Pd-NC(acac)] proceeded with the replacement of the acetylacetonate ligand (acac), affording a dipalladium complex featuring two phosphinosulfonate anions as the O,P-bridges, [(LPd)-Pd-NC(mu(P,O)-Ph(2)PfcCH(2)NHCOC(6)H(4)SO(3))](2), which was structurally characterized by single-crystal X-ray diffraction analysis. All of these Pd(II) complexes, especially compound 8, formed active catalysts for Pd-mediated cross-coupling of aromatic boronic acids with benzoyl chlorides to produce substituted benzophenones in toluene (benzene) water biphasic mixtures. This particular coupling reaction was employed during the preparation of 4'-chloro-4-hydroxybenzophenone, which was in turn converted to fenofibrate, a generic drug widely used to reduce cholesterol levels in blood.
• Practical One-Pot, Three-Component Synthesis of N-Heterocyclic Carbene (NHC) Ligated Palladacycles Derived from <i>N</i>,<i>N</i>-Dimethylbenzylamine
  作者：Eric Assen B. Kantchev、Jackie Y. Ying

  DOI：10.1021/om8008475

  日期：2009.1.12

  Further explorations of the catalytic potential of N-heterocyclic carbene (NHC) ligated palladacycles as catalysts for Pd-mediated transformations have been hampered by the lack of general and practical methods for their synthesis. In this work, we describe a novel, practical approach to NHC-ligated palladacycles by a three-component, one-pot reaction of imidazoliurn salts, PdCl2, and N,N-dimethylbenzylamine in the presence of excess K2CO3 under reflux in reagent-grade acetonitrile in air. 1,3-Diarylimidazolium salts afford the corresponding NHC-Pd(dmba)Cl (dmba = N,N-dimethylbenzylamine-k(2) N,C) complexes in > 80% yield. The conversion of 1,3-diaryl-4,5-dihydroimidazolium and 1,3-dialkylimidazolium or benzimidazolium salts requires the use of stronger base (Cs2CO3) and/or higher temperature (100 degrees C). The Pd-bound chloride anion can be exchanged with silver salts or sodium salts. The NHC-palladacycle adducts have been characterized by single-crystal X-ray crystallography.