fac-trimethyl-iod-(N,N,N',N'-tetramethylethanediamine)palladium(II) | 123147-84-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: fac-trimethyl-iod-(N,N,N',N'-tetramethylethanediamine)palladium(II)
• 英文别名: PdIMe3(N,N,N',N'-tetramethylethylenediamine)；PdIMe3(tmeda)
• CAS: 123147-84-2
• 化学式: C₉H₂₅IN₂Pd
• 分子量: 394.635
• InChiKey: TXUJXDGMBNDSSW-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：

  fac-trimethyl-iod-(N,N,N',N'-tetramethylethanediamine)palladium(II) 以 neat (no solvent, solid phase) 为溶剂， 生成 methyl-iod-(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
• 作为产物：
  描述：

  (N,N,N',N'-tetramethylethylenediamine)dimethylpalladium(II) 在 CH₃I 作用下， 以 丙酮 为溶剂， 以80%的产率得到fac-trimethyl-iod-(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

• Carbon−Oxygen Bond Formation at Organopalladium Centers:  The Reactions of PdMeR(L₂) (R = Me, 4-tolyl; L₂ = tmeda, bpy) with Diaroyl Peroxides and the Involvement of Organopalladium(IV) Species
  作者：Allan J. Canty、Melanie C. Denney、Brian W. Skelton、Allan H. White

  DOI：10.1021/om030644q

  日期：2004.3.1

  PdIVMe3 complexes reductively eliminate Me−Me, and the PdIVMe2Tol complexes eliminate Me−Me and Tol−Me. The resultant Pd(II) complexes PdII(O2CAr)R(L2) react with (ArCO2)2 at higher temperatures to form PdII(O2CAr)2(L2) and R-O2CAr (R = Me, Tol), except for PdII(O2CAr)Tol(tmeda), which forms PdII(O2CAr)2(tmeda) and 4,4‘-bitolyl. Each reaction step has been confirmed by the independent synthesis of intermediates

  第16组氧化剂二苯甲酰基-和双（4-三氟甲基苯甲酰基）-过氧化物与二齿氮供体配体2,2'-联吡啶和N，N，随着温度从-70°C升高，N '，N'-四甲基乙二胺会逐步进行分步处理。碳-氧键在此反应序列中形成，但不是由光谱检测到的那些Pd（IV）络合物形成。初始反应得到未检测到的“ Pd IV（O 2 CAr）2 MeR（L 2）”（Ar = Ph，Ar F ; R = Me，Tol; L 2= bpy，tmeda），立即与Pd II MeR（L 2）进行芳酸甲酯交换，得到Pd II（O 2 CAr）R（L 2）和Pd IV（O 2 CAr）Me 2 R（L 2），其中1 H NMR光谱检测到除Pd IV（O 2 CAr）Me 2 Tol（tmeda）以外的所有产物。在升高温度时，Pd IV Me 3络合物还原性消除Me-Me，而Pd IV Me 2 Tol络合物消除Me-Me和Tol-Me。生成的Pd（II）配合物PdII（O
• Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)
  作者：Bertus A. Markies、Allan J. Canty、Jaap Boersma、Gerard van Koten

  DOI：10.1021/om00017a071

  日期：1994.5

  Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0-degrees-C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:1 ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0-degrees-C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:1 molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) (tmeda) at 0-degrees-C in (CD3)2CO to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50-degrees-C, (CD3)2CO), while benzyl iodide reacts at 40-degrees-C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30-degrees-C in (CD3)2CO to form PdlMe2(CH2Ph)(tmeda), for which H-1 NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from palladium(IV) to platinum(II), palladium(II) to palladium(0), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to tbe higher oxidation state reagent.