methyl-chlor-(N,N,N',N'-tetramethylethanediamine)palladium(II) | 123147-92-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl-chlor-(N,N,N',N'-tetramethylethanediamine)palladium(II)
• 英文别名: (N,N,N',N'-tetramethylethylenediamine)(CH3)PdCl；(N,N,N',N'-tetramethylenediamine)Pd(CH3)Cl；[PdCl(Me)(N,N,N',N'-tetramethylethylenediamine)]；[PdClMe(N,N,N',N'-tetramethylethylenediamine)]；PdMeCl(N,N,N',N'-tetramethylethylenediamine)；[PdCl(Me)(TMEDA)]
• CAS: 123147-92-2
• 化学式: C₇H₁₉ClN₂Pd
• 分子量: 273.114
• InChiKey: CFHLYIRJUTUBHN-UHFFFAOYSA-M

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：

  methyl-chlor-(N,N,N',N'-tetramethylethanediamine)palladium(II) 在 一氧化碳 作用下， 以 氯仿 为溶剂， 以90%的产率得到PdCl(COMe)(N,N,N',N',-tetramethylethanediamine)
  参考文献：
  名称：

  二甲基（N，N，N'，N'-四甲基乙二胺）钯与有机卤化物的反应中的交叉偶联与均相偶联

  摘要：

  DOI：

  10.1021/om00119a019
• 作为产物：
  描述：

  (N,N,N',N'-tetramethylethylenediamine)dimethylpalladium(II) 在 CH₃Cl 作用下， 以 苯 为溶剂， 以50%的产率得到methyl-chlor-(N,N,N',N'-tetramethylethanediamine)palladium(II)
  参考文献：
  名称：

  二甲基（N，N，N'，N'-四甲基乙二胺）钯（II）和二甲基[1,2-双（二甲基膦基）乙烷]钯（II）：合成，X射线晶体结构以及热分解，氧化加成和配体交换反应

  摘要：

  DOI：

  10.1021/om00114a028

文献信息

• Insertion of Imines into Palladium-Acyl Bonds: Towards Metal-Catalyzed Alternating Copolymerization of Imines with Carbon Monoxide To Form Polypeptides
  作者：Smita Kacker、Jang Sub Kim、Ayusman Sen

  DOI：10.1002/(sici)1521-3773(19980518)37:9<1251::aid-anie1251>3.0.co;2-4

  日期：1998.5.18

  From a methyl ligand, CO, and an imine a chelating amide ligand is formed by insertion of the C=N bond into the metal-acyl bond in cationic palladium(II) complexes (see reaction below). The cationic acylpalladium complexes are obtained from CO and readily accessible palladium starting materials. LL=diphosphane ligand.

  由甲基配体，CO和亚胺，通过将C = N键插入阳离子钯（II）配合物中的金属-酰基键中，形成螯合酰胺配体（请参见以下反应）。阳离子酰基铝配合物是从一氧化碳和易于获得的钯原料中获得的。LL ＝二膦配体。
• A dipalladium complex with a single hydroxo bridge and its methylpalladium precursor
  作者：Lingyun Cao、Michael C. Jennings、Richard J. Puddephatt

  DOI：10.1039/b906038c

  日期：——

  The reaction of [PdClMe(Me2NCH2CH2NMe2)] with bis(2-pyridylmethyl)amine, bpma, gave the methylpalladium complex [PdMe(bpma)]Cl, which could be converted to the triflate or tetrafluoroborate salt by reaction with AgOTf or AgBF4. Further reaction of [PdMe(bpma)]OTf with B(C6F5)3 or HOTf gave the complex [Pd2(μ-OH)(bpma)2](OTf)3, which contains a bridging hydroxo ligand and no other bridging ligand, and whose structure contains an unexpectedly large Pd–O–Pd angle of 141.2(3)°. This complex acts as a model for complexes proposed to be formed during hydrolysis in aqueous solution of biologically active compounds such as cisplatin.

  [PdClMe(Me2NCH2CH2NMe2)]与双(2-吡啶甲基)胺（bpma）的反应生成了甲基钯复合物[PdMe(bpma)]Cl，该复合物可以通过与AgOTf或AgBF4反应转化为三氟甲磺酸盐或四氟硼酸盐。[PdMe(bpma)]OTf进一步与B(C6F5)3或HOTf反应生成复合物[Pd2(μ-OH)(bpma)2](OTf)3，该复合物含有桥接的羟基配体且没有其他桥接配体，其结构中意外地出现了一个较大的Pd–O–Pd角度为141.2(3)°。该复合物作为在水溶液中对生物活性化合物（如顺铂）水解过程中形成的复合物的模型。
• Synthesis and Structures of Palladium and Platinum A-Frame Complexes Bridged by a Novel Binucleating Ligand, <i>N</i>,<i>N</i>‘-Bis[(2-diphenylphosphino)phenyl]- formamidine
  作者：Naofumi Tsukada、Osamu Tamura、Yoshio Inoue

  DOI：10.1021/om020003f

  日期：2002.6.1

  homobimetallic complexes. The heterobimetallic complex PdPtMe2(μ-Cl)(μ-dpfam) was obtained by the reaction of PdMeCl(cod) with PtMe(dpfam), which was produced from PtMe2(cod) and Hdpfam. The crystal structures of Pd2Cl2(μ-Cl)(μ-dpfam) and Pt2Me2(μ-Cl)(μ-dpfam) have been determined by X-ray analysis. The results indicate that both complexes have P−M−Cl−M−P A-frame structures, in which each metal center has

  一种新型的双核配体，N，N'-双[（2-二苯基膦基）苯基]甲idine（Hdpfam），已被制备并用于合成同金属和异双金属钯/铂配合物M 2 R 2（μ- X） （μ- dpfam）（M ＝ Pd，Pt； R ＝ Me，p- Tol，Cl； X ＝ Cl，Br，I； dpfam ＝N，N′-双[（2-二苯基膦基）苯基]甲酰胺基）。在tmeda存在下用2当量的MRX（tmeda）或MRX（cod）处理Hdpfam产生了同双金属配合物。异双金属配合物PdPtMe 2（μ通过PdMeCl（cod）与PtMe（dpfam）的反应获得-Cl）（μ-dpfam），后者是由PtMe 2（cod）和Hdpfam产生的。通过X射线分析确定了Pd 2 Cl 2（μ- Cl）（μ- dpfam）和Pt 2 Me 2（μ- Cl）（μ- dpfam）的晶体结构。结果表明这两种配合物均具有P-M-Cl-M-P A框
• Oxidative Addition of Organocobalt(I) and -molybdenum(II) Complexes to Palladium(0) Complexes To Give Heterodinuclear Organometallic Complexes
  作者：Nobuyuki Komine、Hideko Hoh、Masafumi Hirano、Sanshiro Komiya

  DOI：10.1021/om000728o

  日期：2000.12.1

  Oxidative addition of Co(COMe)(CO)4 and MoMeCp(CO)3 to Pd(dba)2 (dba = dibenzylideneacetone) in the presence of the bidentate ligand L2 (L2 = dppe (1,2-bis(diphenylphosphino)ethane), tmeda (N,N,N‘,N‘-tetramethylethylenediamine), bpy (2,2‘-bipyridine), phen (1,10-phenanthroline)) takes place to give L2(MeCO)Pd−Co(CO)4 (L2 = dppe (1), tmeda (2), bpy (3), phen (4)) and (dppe)MePd−MoCp(CO)3 (5), respectively

  在双齿配体L 2（L 2 = dppe（1,2-双（二苯基二膦））存在下，将Co（COMe）（CO）4和MoMeCp（CO）3氧化成Pd（dba）2（dba =二苄叉基丙酮））乙烷），tmeda（N，N，N '，N'-四甲基乙二胺），bpy（2,2'-联吡啶），phen（1,10-菲咯啉））生成L 2（MeCO）Pd-Co （CO）4（L 2 = dppe（1），tmeda（2），bpy（3），phen（4））和（dppe）MePd-MoCp（CO）3（5）， 分别。
• Hydrocarbyl derivatives of dppm- or dppa-bridged alkoxysilyl heterobimetallic Fe–Pd complexes and CO insertion reactions. Crystal structures of [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd(8-mq)] (dppm = Ph2PCH2PPh2), [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppa)PdCl] and [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppa)PdPh] (dppa = Ph2PNHPPh2) †
  作者：Pierre Braunstein、Jérôme Durand、Guido Kickelbick、Michael Knorr、Xavier Morise、Raphael Pugin、Antonio Tiripicchio、Franco Ugozzoli

  DOI：10.1039/a907425b

  日期：——

  The complexes [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdR] (R = alkyl, aryl) have been obtained either by treatment of [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdCl] 1a with organolithium or Grignard reagents or, in the case where R = Me, by reaction of [PdCl(Me)(COD)] (COD = 1,5-cyclooctadiene) with the metallate K[FeSi(OMe)3}(CO)3(dppm-P)] 2a. When dppa was used as an assembling ligand, reaction of the hydrido complex mer-[HFe- Si(OMe)3}(CO)3(dppa-P)] 7b with [PdCl(Me)(COD)] or [Pd(η3-allyl)(µ-Cl)]2 proceeded via elimination of methane or propene, respectively, to afford [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdCl] 1b and not via HCl elimination which would have resulted in hydrocarbyl complexes. However, reaction of 7b with [PdX(R)(TMEDA)] (X = Cl, R = Me; X = I, R = Ph; TMEDA = Me2NCH2CH2NMe2) afforded the hydrocarbyl complexes [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdMe] 3b or [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdPh] 5b. The latter and [(OC)3(MeO)3Si}Fe(µ-dppa)Pd(η3-allyl)] 8b were obtained by reaction of the carbonylmetallate 2b with [PdCl(Me)(COD)], [PdI(Ph)(TMEDA)] or [Pd(η3-allyl)(µ-Cl)]2, respectively. The stabilizing but labile four-membered µ-η2-SiO→Pd bridging interaction facilitates CO insertion into the Pd–Me bond of 3a or 3b to afford the corresponding acetyl complexes. For comparison, [(OC)3(MeO)3Si}Fe(µ-dppm)Pd(8-mq)] 6a which contains a stable five-membered (C,N) chelate at Pd did not insert CO under similar conditions. The reaction of CO with the benzyl derivative [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)Pd(CH2Ph)] 4a was more complex since the resulting acyl [(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdC(O)CH2Ph}] 11a rearranged into the µ-siloxycarbene complex [(OC)3Feµ-C(CH2Ph)OSi(OMe)3}(µ-dppm)Pd(CO)] 12a. Comparisons are made between complexes containing dppm or dppa and different R groups. The structures of complexes 1b, 5b·THF and 6a·hexane have been determined by X-ray diffraction.

  复合物[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdR]（R = 烷基、芳基）是通过用有机锂或格氏试剂处理[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdCl] 1a获得的，或者在R = Me的情况下，通过[PdCl(Me)(COD)]（COD = 1,5-环辛二烯）与金属盐K[FeSi(OMe)3}(CO)3(dppm-P)] 2a反应得到。当使用dppa作为组装配体时，氢化复合物mer-[HFe-Si(OMe)3}(CO)3(dppa-P)] 7b与[PdCl(Me)(COD)]或[Pd(η3-烯丙基)(µ-Cl)]2的反应通过分别消除甲烷或丙烯进行，从而得到[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdCl] 1b，而不是通过消除HCl，这样会导致烃基复合物。然而，7b与[PdX(R)(TMEDA)]（X = Cl, R = Me；X = I, R = Ph；TMEDA = Me2NCH2CH2NMe2）的反应得到烃基复合物[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdMe] 3b或[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppa)PdPh] 5b。后者和[(OC)3(MeO)3Si}Fe(µ-dppa)Pd(η3-烯丙基)] 8b是通过碳酰基金属盐2b与[PdCl(Me)(COD)]、[PdI(Ph)(TMEDA)]或[Pd(η3-烯丙基)(µ-Cl)]2反应获得的。稳定但不稳定的四成员µ-η2-SiO—Pd桥接相互作用促进了CO插入到3a或3b的Pd—Me键中，从而生成相应的乙酰复合物。相比之下，含有在Pd处具有稳定五元(C,N)螯合物的[(OC)3(MeO)3Si}Fe(µ-dppm)Pd(8-mq)] 6a在类似条件下不发生CO插入。与苄基衍生物[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)Pd(CH2Ph)] 4a的CO反应更复杂，因为生成的酰基[(OC)3Feµ-Si(OMe)2(OMe)}(µ-dppm)PdC(O)CH2Ph}] 11a重排为µ-硅氧基碳烯复合物[(OC)3Feµ-C(CH2Ph)OSi(OMe)3}(µ-dppm)Pd(CO)] 12a。对含有dppm或dppa及不同R基团的复合物进行了比较。复合物1b、5b·THF和6a·己烷的结构已通过X射线衍射确定。