cis-[PdCl2(CN{2-Me-6-ClC6H3})2] | 1261236-86-5

• 英文名称: cis-[PdCl2(CN{2-Me-6-ClC6H3})2]
• 英文别名: cis-[PdCl₂(CN{2-Me-6-ClC₆H₃})₂]；cis-[PdCl₂(CN(t-Bu))₂]；cis-[PdCl2(CN(2-Cl-6-Me-C6H3))2]；cis-[PdCl2(CN(2-Cl-6-MeC6H3))2]；cis-[PdCl2(CN-2-Cl-6-MePh)2]2
• CAS: 1261236-86-5
• 化学式: C₁₆H₁₂Cl₄N₂Pd
• 分子量: 480.517
• InChiKey: UWCFXZIBKUBDCG-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(CN{2-Me-6-ClC6H3})2] 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  钯（II）介导的苯二胺加到异氰酸酯中：三种类型的二氨基卡宾配体的生成取决于亲核体的异构结构

  摘要：

  Coupling of the palladium-bis(isocyanide) complexes cis-[PdCl2(CNR)(2)] (R = 2,6-Me2C6H3 1, 2-Cl-6-MeC6H3 2) with benzene-1,3-diamine (BDA1) leads to the diaminocarbene species cis-[PdCl2(CNR){C-(NHR)=NH(1,3-C6H4NH2)}} (5 and 6, respectively). In this reaction, BDA1 behaves as a monofunctional nucleophile that adds to one of the RNC ligands by one amino group. By contrast, the reaction of 1 and 2 with benzene-1,4-diamine (BDA2) involves both amino functionalities of the diamine and leads to the binuclear species [cis-PdCl2(CNR){mu-C(NHR)=NH(1,4-C6H4)NH=C-(NHR)}-(cis)-PdCl2(CNR)] (6 and 7) featuring two 1,4-bifunctional diaminocarbene ligands. The reaction of cis-[PdCl2(CNR)(2)] (R = cyclohexyl 3) with either BDA1 or BDA2 does not afford any isolable carbene derivatives. The most versatile chemistry was observed when 1-3 were treated with benzene-1,2diamine (BDA3) and the relevant substituted 1,2-diamines, viz., 4,5-dimethylbenzene-1,2-diamine (BDA4) and 4,5-clichlorobenzene-1,2-diamine (BDAS). The addition of these diamines brings about the formation of the monocarbene cationic complexes cis-[PdCl(CNR){C(NHR)=NHC6H2X2NH2}]Cl (X = H, Me, CO (8-16), the Chugaev-type C,C-bound bis-carbenes cis-[PdCl2{C(NHR)=NHC6H2X2NH=C(NHR)}] (17, 18), and the bis(C,N-chelated)carbene complexes cis-{Pd{C(NHR)=NHC6H2X2NH2}(2)]Cl-2 (19-24). All prepared complexes (with the exception of 17 and 18) were isolated as colorless or pale yellow solids and characterized by elemental analyses (C, H, N), HRESI +/--MS, IR, H-1 and C-13{H-1} NMR spectroscopies, and 4, 7, 13, 16, and 24 by X-ray diffraction. Complexes 17 and 18 were characterized by HRESI +/--MS and IR spectroscopy, and their structures were established by X-ray crystallography.

  DOI：

  10.1021/acs.organomet.5b00936
• 作为产物：
  描述：

  2-氯-6-苯甲基异氰 、 bis(acetonitrile)palladium(II) chloride 以 氯仿 为溶剂， 以87%的产率得到cis-[PdCl2(CN{2-Me-6-ClC6H3})2]
  参考文献：
  名称：

  金属二氨基卡宾的新型反应模式：钯（II）介导的无环二氨基卡宾与异腈之间的偶联导致双核物种。

  摘要：

  金属-介导的等摩尔量的间耦合顺- [的PdCl 2（CNR 1）2 ] [R 1 = 2,6-ME 2 ç 6 ħ 3（的Xyl）1，2-CL，6-ME-C 6 H ^ 3 2，环己基（Cy）3 ]和H 2 NC 5 H 3 R 2 N [R 2 = H，2-氨基吡啶4；[R 2 = NH 2，2,6-二氨基吡啶5]在20–25°C下平稳进行12 h，并生成二氨基卡宾物质[PdCl { C（NHC 5 H 3 R 2 N）═N（H）R 1 }（CNR 1）] Cl（6 – 9） 。在2与5的反应中（摩尔比为1：1），仅通过高分辨率ESI + -MS在与其他尚未鉴定的产物的混合物中检测到相应的卡宾10。的每一个的另外6 - 8到开始1或2在过量固体K的存在：（1摩尔比1）2 CO3在CHCl 3中，并将反应混合物在40°C下加热12 h，得到一种新型的双核配合物，分别为11（75％的分离产率

  DOI：

  10.1021/om2002574

文献信息

• Selective Nucleophilic Oxygenation of Palladium-Bound Isocyanide Ligands: Route to Imine Complexes That Serve as Efficient Catalysts for Copper-/Phosphine-Free Sonogashira Reactions
  作者：Andreii S. Kritchenkov、Konstantin V. Luzyanin、Nadezhda A. Bokach、Maxim L. Kuznetsov、Vladislav V. Gurzhiy、Vadim Yu. Kukushkin

  DOI：10.1021/om4000665

  日期：2013.3.25

  in excellent yields (90–94%), while the reaction of the cis-[PdCl2(CNR)2] complexes with aldonitrones proceeds as 1,3-dipolar cycloaddition, giving carbene adducts which then convert to the imine complexes. Theoretical calculations at the DFT level indicate that, in the case of aldonitrones, formation of the imine complexes occurs preferably via a cycloaddition/splitting pathway, including the generation

  顺式[PdCl 2（CNR）2 ]之间的金属介导反应（R = Xy（1），Cy（2），t Bu（3），C 6 H 3（Cl-2）Me-6（4））和酮基硝酮博士2 C = N（O）C 6 H ^ 4 R'（R'=我（5），CL（6））继续进行以1：1的摩尔比选择性亲核氧合，并提供该亚胺胩配合物[的PdCl 2 N（C 6 H ^ 4 R'）═CPh 2 }（CNR）]（7– 14：R'= Me，R = Xy（7），Cy（8），t Bu（9），C 6 H 3（Cl-2）Me-6（10）；R'= Cl，R = Xy（11），Cy（12），t Bu（13），C 6 H 3（Cl-2）Me-6（14）），产率极高（90-94％），而所述的反应顺式- [的PdCl 2（CNR）2 ]配合物醛硝酮以1,3-偶极环加成反应进行，生成卡宾加合物，然后将其转化为亚胺配合物。DFT水平的理论计算表明，在醛基亚
• Reaction of o-aminophenol and o-aminobenzyl alcohol with palladium(II) bis(isocyanide) complexes
  作者：M. A. Kinzhalov、G. L. Starova、M. Haukka、V. P. Boyarskii

  DOI：10.1134/s1070363216100170

  日期：2016.10

  Reactions of palladium(II) bis-isocyanide complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3, 2-Me-6-ClC6H3) with an equimolar amount of chelating N,O-binucleophiles, 2-aminophenol and (2-aminophenyl)-methanol, in acetonitrile at room temperature in 24 h selectively afforded the corresponding open-chain monocarbene complexes. The complexation involved one isocyanide ligand and amino group of the aromatic

  钯（II）双-异氰化物配合物顺式-[PdCl 2（CNR）2 ]（R = 2,6-Me 2 C 6 H 3，2 -Me-6-ClC 6 H 3）的反应在室温下于24小时内在乙腈中螯合N，O-双亲核试剂，2-氨基苯酚和（2-氨基苯基）-甲醇，有选择地提供了相应的开链单碳烯配合物。络合涉及一个异氰酸酯配体和芳香胺的氨基。双（卡宾）配合物（在苛刻条件下与4当量亲核试剂的反应中）和C，O-检测到螯合物的结构。分离的配合物通过元素分析，IR，NMR和质谱以及X射线衍射数据进行表征。
• Metal-mediated coupling of amino acid esters with isocyanides leading to new chiral acyclic aminocarbene complexes
  作者：Tatyana B. Anisimova、M. Fátima C. Guedes da Silva、Vadim Yu. Kukushkin、Armando J. L. Pombeiro、Konstantin V. Luzyanin

  DOI：10.1039/c4dt01917b

  日期：——

  Metal-mediated coupling between equimolar amounts of cis-[PdCl2(CNR1)2] (1–5) and the amino acid esters L-HTyrOMe (7) or L-HProOtBu (8) proceeds at 40 °C in chloroform over ca. 6 h. The subsequent workup affords the complexes cis-[PdCl2(CNR1)C(TyrOMe)NHR1}] (R1 = Xyl 9, 2-Cl-6-Me-C6H310) or cis-[PdCl2(CNR1)C(ProOtBu)NHR1}] (R1 = Xyl 11, 2-Cl-6-Me-C6H312, Cy 13, tBu 14, 2-naphthyl 15) in good to excellent isolated yields (75–94%). The corresponding reaction between trans-[PdI2(CNR1)2] (6) and 8 brings about the formation of trans-[PdI2(CNCy)C(ProOtBu)NHCy}] (16, 76% isolated yield). The reaction of 6 with 7 proceeds non-selectively giving a broad mixture of products. Complexes 9–16 were characterized by elemental analyses (C, H, N), ESI+/−-MS, IR, 1D (1H, 13CH}) and 2D (1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopic techniques, and by single-crystal X-ray diffraction (for 9, 11–13, and 16).

  金属介导的反应在氯仿中以等摩尔量的 cis-[PdCl2(CNR1)2] (1–5) 和氨基酸酯 L-HTyrOMe (7) 或 L-HProOtBu (8) 在 40°C 下进行，约需 6 小时。后续的处理可以获得复合物 cis-[PdCl2(CNR1)C(TyrOMe)NHR1}] (R1 = Xyl 9, 2-Cl-6-Me-C6H310) 或 cis-[PdCl2(CNR1)C(ProOtBu)NHR1}] (R1 = Xyl 11, 2-Cl-6-Me-C6H312, Cy 13, tBu 14, 2-萘基 15)，其分离收率良好至优秀（75–94%）。与 trans-[PdI2(CNR1)2] (6) 和 8 的反应生成 trans-[PdI2(CNCy)C(ProOtBu)NHCy}] (16，分离收率 76%)。6 与 7 的反应进行非选择性反应，产生一系列宽广的产物混合物。复合物 9–16 通过元素分析（C, H, N）、ESI+/−-质谱、红外光谱、1D（1H, 13CH}）和 2D（1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC）核磁共振光谱技术以及单晶 X 射线衍射（对于 9, 11–13 和 16）进行表征。
• Diversity of Isomerization Patterns and Protolytic Forms in Aminocarbene Pd^II and Pt^II Complexes Formed upon Addition of <i>N</i>,<i>N</i>′-Diphenylguanidine to Metal-Activated Isocyanides
  作者：Svetlana A. Katkova、Mikhail A. Kinzhalov、Peter M. Tolstoy、Alexander S. Novikov、Vadim P. Boyarskiy、Anastasiia Yu. Ananyan、Pavel V. Gushchin、Matti Haukka、Andrey A. Zolotarev、Alexander Yu. Ivanov、Semen S. Zlotsky、Vadim Yu. Kukushkin

  DOI：10.1021/acs.organomet.7b00569

  日期：2017.11.13

  2-Cl-6-MeC6H3, cyclohexyl (Cy), t-Bu, C(Me)2CH2(Me)3 (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC6H3, Cy, t-Bu, and tmbu] with N,N′-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated

  钯（II）和铂（II）异氰化物配合物的反应顺式-[MCl 2（CNR）2 ] [M = Pd，R = C 6 H 3（2,6-Me 2）（Xyl），2-Cl -6-MeC 6 H 3，环己基（Cy），t- Bu，C（Me）2 CH 2（Me）3（1,1,3,3-四甲基丁-1-基缩写为tmbu）；M = Pt，R = Xyl，2-Cl-6-MeC 6 H 3，Cy，t- Bu和tmbu]，其中N，N'-二苯基胍（DPG）导致DPG衍生的金属结合的去质子化的无环二氨基卡宾（ADC）物种。该反应通过两步过程进行，包括将胍与一种异氰酸酯进行初始偶联，并导致去质子化的单卡宾单螯合物质，而下一次添加则得到去质子化的双卡宾双螯合金属化合物。DPG表现为亲核试剂，去质子化碱基和螯合剂。DPG的添加以不同的区域选择性进行，这取决于金属中心，并且在更大程度上取决于RNC中的取代基R。对去质子化的单-和双-卡宾
• ADC-Based Palladium Catalysts for Aqueous Suzuki–Miyaura Cross-Coupling Exhibit Greater Activity than the Most Advantageous Catalytic Systems
  作者：Mikhail A. Kinzhalov、Konstantin V. Luzyanin、Vadim P. Boyarskiy、Matti Haukka、Vadim Yu. Kukushkin

  DOI：10.1021/om4007592

  日期：2013.9.23

  The reaction between the equimolar amounts of cis-[PdCl2(CNR1)(2)] (R-1 = cyclohexyl (Cy) (1), tBu (2)) and the carbohydrazides (RCONHNH2)-C-2 (R-2 = Ph (5), 4-ClC6H4 (6), 3-NO2C6H4 (7), 4-NO2C6H4 (8), 4-CH3C6H4 (9), 3,4-(MeO)(2)C6H3 (10), naphth-1-yl (11), fur-2-yl (12), 4-NO2C6H4CH2 (13), Cy (14), 1-(4-fluorophenyl)-5-oxopyrrolidin-3-yi (15), (pyrrolidin-1-yl)C(0) (16)) proceeds in refluxing CHCl3 for ca. 4 h. A subsequent workup provided the amino-carbene species cis-[PdCl2C(NHNHC(O)R-2)=N(H)R-1}-(CNR1)] (18-33) in good to excellent (80-95%) isolated yields. The coupling of equimolar amounts of cis-[PdCl2(CNR1)(2)] (R-1 = Cy (1), tBu (2), 2,6-Me2C6H3 (XYI) (3), 2-Cl-6-MeC6H3 (4)) and PhSO2NHNH2 (17) occurs similarly and affords the aminocarbenes cis-[PdCl2C(NHNHS(O)(2)Ph)=N(H)R-1}(CNR1)] (34-37; 60-90%). Complexes 18-37 were characterized by elemental analyses (C, H, N), ESV+-MS, IR, and 1D (H-1, C-13H-1}) and 2D (H-1,H-1-COSY, H-1,C-13-HMQC, H-1,C-13-HSQC, HMBC) NMR spectroscopy, as well as by X-ray diffraction for three species (34, 37, and 38). The catalytic properties of 18-37 in Suzuki Miyaura cross-coupling in aqueous medium were evaluated, and 18-37 showed remarkable activity (0.001-0.01 mol % catalyst loading). The scope of the catalytic process covers sterically unhindered and sterically demanding aryl bromides and aryl iodides bearing donor and/or acceptor substituents and activated aryl chlorides. All organohalides reacted with a range of arylboronic acids at 80 degrees C within 2 h (100 degrees C and 3 h for the chlorides), providing target diaryis in yields up to 99% and with maximum TONs of 9.9 X 10(3) (for aryl iodides), 4.7 X 104 (for aryl bromides), and 9.2 X 10(3) (for aryl chlorides).