[Ru(Cl)(Me)(CO)2(N,N'-di-isopropyl-1,4-diaza-1,3-butadiene)] | 157378-34-2

• 英文名称: [Ru(Cl)(Me)(CO)2(N,N'-di-isopropyl-1,4-diaza-1,3-butadiene)]
• 英文别名: Ru(CO)2(CH3)(Cl)(1,4-diisopropyl-1,4-diaza-1,3-butadiene)；trans,cis-RuCl(Me)(CO)2(i-PrNCHCHN-i-Pr)；[Ru(Cl)(Me)(CO)2(iPr-DAB)]；[Ru(Cl)(Me)(CO)2(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)]；[Ru(Cl)(CH3)(CO)2(N,N'-diisopropyl-1,4-diazabutadiene)]；RuCl(CH3)(CO)2(N,N'-diisopropyl-1,4-diaza-butadiene)
• CAS: 157378-34-2
• 化学式: C₁₁H₁₉ClN₂O₂Ru
• 分子量: 347.807
• InChiKey: RKRGIIKKRROVIX-YYSZEHGHSA-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：

  [Ru(Cl)(Me)(CO)2(N,N'-di-isopropyl-1,4-diaza-1,3-butadiene)] 在 P(C₆H₅)3 作用下， 以 氘代氯仿 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  Ru(CO)4(PMe2Ph) Catalyzed Carbonylation of Ru(CH3)I(CO)2(iPr-DAB) and Ru(CH3)I(CO)2(iPr-Pyca) Complexes. X-ray Structure of [Ru(CH3)(CO)2[(2-methoxyethyl)Pyca]][OTf]

  摘要：

  The synthesis and characterization of complexes Ru(R)X(CO)2(R'-Pyca) (R = CH3 and X = 1 (2); R = C(O)CH3 and X = I (3); R = CH3 and X = OTf = SO3CF3 (4); R = C(O)CH3 and X = OTf (5); R1-Pyca = 2-R1-pyridinecarbaldimine; and R' = isopropyl (b), methoxyethyl (c), or isopropoxypropyl (d)), respectively, will be presented. The X-ray structure determination of the yellow crystals of [Ru(CH3)(CO)2(CH3OCH2CH2-Pyca)][OTf] (4c) has been carried out. Crystal data for 4c. monoclinic, space group P2(1)/c with a = 8.5008(4) angstrom, b = 12.3281(8) angstrom, c = 18.412(1) angstrom, beta = 01.118(6)-degrees, V = 1893.4(2) angstrom3, z = 4. The Ru(CO)4(PMe2Ph) (13) catalyzed CO insertion in the methyl-ruthenium bond of Ru(CH3)X(CO)2(iPr-DAB) (X = I (2a); X = OTf (4a); X = Cl (6a); DAB = 1,4-diaza-1,3-butadiene) and Ru(CH3)X(CO)2(iPr-Pyca) (X = I (2b); X = OTf (4b)) has been studied by use of labeled Ru((CO)-C-13)4(PMe2Ph) (13) and by reaction in the absence or presence of additional ligand PPh3 and CO. For the neutral complexes 2a, 6a, and 2b the key intermediate for the CO insertion catalyzed by 13 is most probably of the type [Ru(CH3)X(CO)(alpha-diimine)Ru(CO)3(PMe2Ph)(mu-CO)2] (X1), which is, however, not observed during the reaction. By (CO)-C-13 labeling experiments it has clearly been demonstrated that binuclear species are involved in this reaction. Complex Ru(CO)4(PMe2Ph) (13) decomposes in CDCl3 at 45-degrees-C under N2 and under a CO atmosphere (1 and 8 atm) within 3 h to form Ru2(CO)4(PMe2Ph)2(mu-Cl)2 (15), which can further react with PPh3 to Ru2(CO)4(PMe2Ph)2(PPhs)2(mu-Cl)2 (16). Suprisingly, 13 is stable under high CO pressure in the presence of 2a, 6a, and 2b in CDCl3 at 45-degrees-C for several hours, most probably as a result of a faster reaction of Ru(CO)4(PMe2Ph) (13) or most likely [Ru(CO)3(PMe2Ph)] with 2a, 6a, or 2b than with CDCl3, which prohibits decomposition.

  DOI：

  10.1021/om00020a046
• 作为产物：
  描述：

  以 正庚烷 为溶剂， 以100%的产率得到[Ru(Cl)(Me)(CO)2(N,N'-di-isopropyl-1,4-diaza-1,3-butadiene)]
  参考文献：
  名称：

  Ru(CO)4(PMe2Ph) Catalyzed Carbonylation of Ru(CH3)I(CO)2(iPr-DAB) and Ru(CH3)I(CO)2(iPr-Pyca) Complexes. X-ray Structure of [Ru(CH3)(CO)2[(2-methoxyethyl)Pyca]][OTf]

  摘要：

  The synthesis and characterization of complexes Ru(R)X(CO)2(R'-Pyca) (R = CH3 and X = 1 (2); R = C(O)CH3 and X = I (3); R = CH3 and X = OTf = SO3CF3 (4); R = C(O)CH3 and X = OTf (5); R1-Pyca = 2-R1-pyridinecarbaldimine; and R' = isopropyl (b), methoxyethyl (c), or isopropoxypropyl (d)), respectively, will be presented. The X-ray structure determination of the yellow crystals of [Ru(CH3)(CO)2(CH3OCH2CH2-Pyca)][OTf] (4c) has been carried out. Crystal data for 4c. monoclinic, space group P2(1)/c with a = 8.5008(4) angstrom, b = 12.3281(8) angstrom, c = 18.412(1) angstrom, beta = 01.118(6)-degrees, V = 1893.4(2) angstrom3, z = 4. The Ru(CO)4(PMe2Ph) (13) catalyzed CO insertion in the methyl-ruthenium bond of Ru(CH3)X(CO)2(iPr-DAB) (X = I (2a); X = OTf (4a); X = Cl (6a); DAB = 1,4-diaza-1,3-butadiene) and Ru(CH3)X(CO)2(iPr-Pyca) (X = I (2b); X = OTf (4b)) has been studied by use of labeled Ru((CO)-C-13)4(PMe2Ph) (13) and by reaction in the absence or presence of additional ligand PPh3 and CO. For the neutral complexes 2a, 6a, and 2b the key intermediate for the CO insertion catalyzed by 13 is most probably of the type [Ru(CH3)X(CO)(alpha-diimine)Ru(CO)3(PMe2Ph)(mu-CO)2] (X1), which is, however, not observed during the reaction. By (CO)-C-13 labeling experiments it has clearly been demonstrated that binuclear species are involved in this reaction. Complex Ru(CO)4(PMe2Ph) (13) decomposes in CDCl3 at 45-degrees-C under N2 and under a CO atmosphere (1 and 8 atm) within 3 h to form Ru2(CO)4(PMe2Ph)2(mu-Cl)2 (15), which can further react with PPh3 to Ru2(CO)4(PMe2Ph)2(PPhs)2(mu-Cl)2 (16). Suprisingly, 13 is stable under high CO pressure in the presence of 2a, 6a, and 2b in CDCl3 at 45-degrees-C for several hours, most probably as a result of a faster reaction of Ru(CO)4(PMe2Ph) (13) or most likely [Ru(CO)3(PMe2Ph)] with 2a, 6a, or 2b than with CDCl3, which prohibits decomposition.

  DOI：

  10.1021/om00020a046

文献信息

• Photochemical bond homolysis in a novel series of metal-metal bonded complexes Ru(E) (E′) (CO)2(iPr-DAB)
  作者：Maxim P. Aarnts、Derk J. Stufkens、Antonín Viček

  DOI：10.1016/s0020-1693(97)05530-8

  日期：1997.12

  108s−1) for complexes which contain RuMe, RuMn or RuRe bonds. Bond homolysis in these species is highly selective, since only RuMe, RuMn and RuRe bond splitting was observed for Ru(Me) (SnPh3) (CO)2(iPr-DAB), Ru(SnPh3) (Mn(CO)5)(CO)2(iPr-DAB), respectively. The photoproduced [Ru(E) (CO)2(iPr-DAB)] radicals were detected by time resolved UV-Vis spectroscopy on a timescale 10 ns-100 μs. The [Ru(SnPh3)

  顺式-顺式-Ru（E）（E'）（CO）2（iPr-DAB）（ECl，SnPh 3，PbPh 3，Mn（CO）5，Re（CO）5，Me;的配合物的光化学发现E'（取决于E）＝ SnPh 3，PbPh 3，GePh 3，Mn（CO）5，Re（CO）5）强烈依赖于轴向配体E和E'的组合和特征。Ru（Cl）（SnPh 3）（CO）2（iPr-DAB）和Ru（Cl）（PbPh 3）（CO）2除外（iPr-DAB）几乎没有反应性，Ru-E / E'键之一在辐照时被同质分解为复合物的最低能量吸收带。对于钌（SnPh 3）2（CO）2（IPR-DAB），从热平衡发生此反应3 σπ *激发态具有2.3×10的速率常数5小号-1和温度相关的量子产率（Ë n = 1450 cm -1）。非选择性Ru＆.zsbdnd; Ru（SnPh 3）（GePh 3）（CO）2的（40％）和Ru-Sn（40％）键均质-（i
• Syntheses, structures and spectroscopic properties of a novel series of metalmetal bonded complexes Ru(E)(E′)(CO)2(iPrDAB): (E  Br, E′  Mn(CO)5; E  SnPh3, E′  Mn(CO)5, Re(CO)5, CO(CO)4; E  Me, E′  Re(CO)5; E  E′  Mn(CO)5, Re(CO)5; iPrDAB  N,N′-diisopropyl-1,4-diaza-1,3-butadiene)
  作者：Maxim P. Aarnts、Ad Oskam、Derk J. Stufkens、Jan Fraanje、Kees Goubitz、Nora Veldman、Anthony L. Spek

  DOI：10.1016/s0022-328x(96)06726-5

  日期：1997.3

  describes the syntheses, structures and spectroscopic (IR, Raman, NMR, visible absorption) properties of novel metalmetal bonded complexes of the type trans,cis-Ru(E)(E′)(CO)2(iPrDAB) in which E  Br, Me, SnPh3, Mn(CO)5 or Re(CO)5 and E′  Mn(CO)5, Re(CO)5 or Co(CO)4 (depending on E). The structures of Ru(SnPh3)(Mn(CO)5)(CO)2(iPrDAB) Ru(SnPh3)(Co(CO)4)(CO)2(iPrDAB) and Ru(Re(CO)5)2(CO)2(iPrDAB) were determined

  本文介绍的合成，结构和光谱（IR，拉曼光谱，NMR，可见光吸收）的类型的新颖metalmetal结合复合物性质的反式，顺式-Ru（E）（E'）（CO）2（我Pr DAB），其中EBr，Me，SnPh 3，Mn（CO）5或Re（CO）5和E'Mn（CO）5，Re（CO）5或Co（CO）4（取决于E） 。茹（SnPh的结构3）（锰（CO）5）（CO）2（我PrDAB）的Ru（SnPh 3）（CO（CO）4）（CO）2（我PrDAB）和Ru（稀土（CO）5）2（CO）2（我PrDAB）通过单晶X射线衍射来确定。配合物具有扭曲的八面体几何形状，且在轴向位置具有E和E'。的Ru（SnPh结构3）（CO（CO）4）（CO）2（我PrDAB）值得注意的是，由于钴（CO）的羰基配位体中的一个4种形式的半桥茹。在ν（CO）和IR和拉曼光谱ν小号（CN）波数区域被分配。吸收光谱在可见光区域显示一
• Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]
  作者：Heleen A. Nieuwenhuis、Annelies van Loon、Marieke A. Moraal、Derk J. Stufkens、Ad Oskam、Kees Goubitz

  DOI：10.1016/0022-328x(94)05300-z

  日期：1995.5

  Photochemical reactions are reported for the metal-metal-bonded complexes [(CO)(5)Mn-Ru(Me)(CO)(2)(alpha-diimine)] [alpha-diimine = pyridine-2-carbaldehyde-N-isopropylimine (Pr-i-PyCa), N,N'-diisopropyl-1,4-diaza-1,3-butadiene (Pr-i-DAB)] upon irradiation into their lowest-energy absorption band. The radicals [Mn(CO)(5)] and [Ru(Me)(CO)(2)(alpha-diimine)] ' are formed by homolytic splitting of the Mn-Ru bond; the latter radicals have been characterized by ESR spectroscopy. In THF, the [Ru(Me)(CO)(2)(Pr-i-DAB)] radicals dimerize to give [Ru(Me)(CO)(2)(Pr-i-DAB)](2), and the corresponding radicals from the Pr-i-PyCa complex gave an unidentified product. Irradiation of a solution of the complexes in CH2Cl2 or CHCl3 afforded [Mn(Cl)(CO)(5)] and [Ru(Cl)(Me)(Co)(2)(alpha-diimine)] but in apolar solvents such as hexane, completely different photoproducts, viz. [(CO)(3)Mn-mu-(sigma(N),sigma(N'),eta(2) (CN),eta(2)(C'N')-Pr-i-DAB)RU(Me)(CO)(2)] and [(CO)(4)Mn-mu-(sigma(N),sigma(N'),eta(2)(CN)-Pr-i-PyCa)Ru(Me)(CO)(2)] were obtained. The crystal structure of the last complex was determined.The photochemical quantum yield for the disappearance of the Pr-i-DAB complex was ca. 0.30, but only 0.05 for the Pr-i-PyCa complex. Low-temperature measurements and flash photolysis data showed that this difference in behaviour is due to the thermal instability of the dimer [Ru(Me)(CO)(2)(Pr-i-PyCa)](2), which leads to partial regeneration of the parent complex at room temperature. At temperatures below 163 K, the photodecomposition into radicals was followed by electron transfer, leading to formation of the ions [(CO)(5)Mn](-) and [Ru(Me)(S)(CO)(2)(alpha-diimine)](+) in 2-MeTHF and the contact ion-pair [(COMn-... Ru(Me)(CO)(2)(alpha-diimine)(+)] in 2-chlorobutane. Similar photodisproportionation products were formed upon irradiation of the complexes at room temperature in the presence of N- or P-donor ligands.
• Nieuwenhuis, Heleen A.; Stufkens, Derk J.; Oskam, Ad, Inorganic Chemistry, 1994, vol. 33, # 15, p. 3212 - 3217
  作者：Nieuwenhuis, Heleen A.、Stufkens, Derk J.、Oskam, Ad

  DOI：——

  日期：——