[Me2NC(N(i)Pr)2Cu]2 | 870990-61-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [Me2NC(N(i)Pr)2Cu]2
• 英文别名: [Me2NC(iPrN)2Cu]2；copper (I) 2-dimethylamino-1,3-diisopropylamidinate；copper(1+);(N,N-dimethyl-N'-propan-2-ylcarbamimidoyl)-propan-2-ylazanide
• CAS: 870990-61-7
• 化学式: C₁₈H₄₀Cu₂N₆
• 分子量: 467.648
• InChiKey: UUMJYKWVJARERP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  33.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Me2NC(N(i)Pr)2Cu]2 生成 1,1-Dimethyl-2-propan-2-yl-3-propan-2-ylideneguanidine
  参考文献：
  名称：

  Gas-Phase Thermolysis of a Guanidinate Precursor of Copper Studied by Matrix Isolation, Time-of-Flight Mass Spectrometry, and Computational Chemistry

  摘要：

  The fragmentation of the copper(I) guanidinate [Me2NC(NiPr)(2)CU](2) (1) has been investigated with time-of-flight mass spectrometry (TOF IVIS), matrix-isolation FTIR spectroscopy (MI FTIR spectroscopy), and density functional theory (DFT) calculations. Gas-phase thermolyses of 1 were preformed in the temperature range of 100-800 degrees C. TOF IVIS and MI FTIR gave consistent results, showing that precursor 1 starts to fragment at oven temperatures above 150 degrees C, with a close to complete fragmentation at 260 degrees C, Precursor 1 thermally fragments to Cu-(s), H-2(g), and the oxidized guanidine Me2NC(=NiPr)(N=CMe2) (3). In TOF MS experiment, 3 was clearly indentified by its molecular ion at 169.2 u. Whereas H-2(+) was detected, atomic Cu was not found in gas-phase thermolysis. In addition, the guanidine Me2NC(NiPr)(NHiPr) (2) was detected as a minor component among the thermolysis products. MI thermolysis experiments with precursor 1 were performed, and species evolving from the thermolysis oven were trapped in solid argon at 20 K. These species were characterized by FTIR spectroscopy. The most indicative feature of the resulting spectra from thermolysis above 150 degrees C was a set of intense and structured peaks between 1600 and 1700 cm(-1), an area where precursor 1 does not have any absorbances. The guanidine 2 was matrix-isolated, and a comparison of its FTIR spectrum with the spectra of the thermolysis of 1 indicated that species 2 was among the thermolysis products. However, the main IR bands in the range of 1600 and 1700 cm(-1) appeared at 1687.9, 1668.9, 1635.1, and 1626.6 cm(-1) and were not caused by species 2. The oxidized guanidine 3 was synthesized for the first time and characterized by H-1 NMR and FTIR spectroscopy. A comparison of an FTIR spectrum of matrix isolated 3 with spectra of the thermolysis of 1 revealed that the main IR bands in the range of 1600 and 1700 cm(-1) are due to the presence of 3. The isomers exhibit the NMe2 group cis or trans to the iPr group, with cis-3 being significantly less stable than trans-3. At higher temperature secondary thermal fragments had been observed. For example at 700 degrees C, TOF MS and MI FTIR data showed that species 2 and 3 both eliminate HNMe2 to give the carbodiimides iPrNCN/Pr (CDI) and iPrNCN[C(=CH2)Me] (4), respectively. A DIFT study of the decomposition of compound 1 was undertaken at the B3LYP/6-31 +G(d,p) level of theory employing dispersion-correcting potentials (DCPs). The DFT study rationalized both carbodiimide deinsertion and P-hydrogen elimination as exergonic decomposition pathways (Delta G = -44.4 kcal/mol in both cases), but experiment showed beta-hydrogen elimination to be the favorable route.

  DOI：

  10.1021/ic902247w
• 作为产物：
  描述：

  lithium dimethylamide 、 copper(l) chloride 以 四氢呋喃 为溶剂， 反应 1.0h， 以60%的产率得到[Me2NC(N(i)Pr)2Cu]2
  参考文献：
  名称：

  COPPER (I) COMPOUNDS USEFUL AS DEPOSITION PRECURSORS OF COPPER THIN FILMS

  摘要：

  铜（I）胺基酸盐前体用于制造半导体器件中形成铜薄膜，以及使用化学气相沉积或原子层沉积过程在基板上沉积铜（I）胺基酸盐前体的方法。

  公开号：

  US20050281952A1

文献信息

• Synthesis and Thermal Chemistry of Copper (I) Guanidinates
  作者：Jason P. Coyle、Wesley H. Monillas、Glenn P. A. Yap、Seán T. Barry

  DOI：10.1021/ic701317y

  日期：2008.1.1

  Copper (1) guanidinate dimers were generated by a salt metathesis route and structurally characterized. The guanidinates differed from the known amidinate dimers because of a large torsion of the dimer ring. This had a direct effect on their thermal chemistry. The thermal reactivity was investigated by several methods, including a novel temperature-resolved, gas-phase method that was monitored by mass spectrometry. The copper guanidinates underwent carbodiimide deinsertion to produce copper metal at temperatures between 225 -and 250 degrees C in the gas phase and at 125 degrees C in solution. The amidinate investigated also showed copper deposition at 190 degrees C in the gas phase, and 135 degrees C in solution, but without carbodiimide deinsertion. The guanidinate compounds deposited crystalline copper at 225 degrees C in a simple chemical vapor deposition experiment.
• Copper Iminopyrrolidinates: A Study of Thermal and Surface Chemistry
  作者：Jason P. Coyle、Peter J. Pallister、Agnieszka Kurek、Eric R. Sirianni、Glenn P. A. Yap、Seán T. Barry

  DOI：10.1021/ic3021035

  日期：2013.1.18

  Several copper(I) iminopyrrolidinates have been evaluated by thermogravimetric analysis (TGA) and solution based H-1 NMR studies to determine their thermal stability and decomposition mechanisms. Iminopyrrolidinates were used as a ligand for copper(I) to block previously identified decomposition routes of carbodiimide deinsertion and beta-hydrogen abstraction. The compounds copper(I) isopropyl-iminopyrrolidinate (1) and copper(I) tert-butyl-iminopyrrolidinate (2) were synthesized for this study, and compared to the previously reported copper(I) tert-butyl-imino-2,2-dimethylpyrrolidinate (3) and the copper(I) guanidinate [Me2NC((PrN)-Pr-1)(2)Cu](2) (4). Compounds 1 and 2 were found to be volatile yet susceptible to decomposition during TGA. At 165 degrees C in C6D6, they had half-lives of 181.7 h and 23.7 h, respectively. The main thermolysis product of 1 and 2 was their respective protonated iminopyrrolidine ligand. beta-Hydrogen abstraction was proposed for the mechanism of thermal decomposition. Since compound 3 showed no thermolysis at 165 degrees C, it was further studied by chemisorption on high surface area silica. It was found to eliminate an isobutene upon chemisoption at 275 degrees C. Annealing the sample at 350 degrees C showed further evidence of the decomposition of the surface species, likely eliminating ethene, and producing a surface bound methylene diamine.