(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)Ru(CO)2(trans-Cl)2 | 200701-72-0

• 英文名称: (N,N'-diisopropyl-1,4-diaza-1,3-butadiene)Ru(CO)2(trans-Cl)2
• 英文别名: [Ru(Cl)2(CO)2(N,N'-di-isopropyl-1,4-diaza-1,3-butadiene)]；Ru(CO)2(Cl)2(1,4-diisopropyl-1,4-diaza-1,3-butadiene)；RuCl2(CO)2(N,N'-diisopropyl-1,4-diaza-butadiene)；trans,cis-RuCl2(CO)2(i-PrNCHCHN-i-Pr)；cis(CO,CO),trans(Cl,Cl)-[Ru(Cl)2(CO)2(N,N'-diisopropyl-1,4-diazabutadiene)]；[Ru(Cl)2(CO)2(iPr-DAB)]
• CAS: 200701-72-0；245738-91-4
• 化学式: C₁₀H₁₆Cl₂N₂O₂Ru
• 分子量: 368.225
• InChiKey: NXVJSNSRGWZOSI-YYSZEHGHSA-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：

  甲醇 、 (N,N'-diisopropyl-1,4-diaza-1,3-butadiene)Ru(CO)2(trans-Cl)2 以 甲醇 为溶剂， 以99%的产率得到(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)Ru(CO)(CH3OH)(trans-Cl)2
  参考文献：
  名称：

  Comparing structures and reactivity in analogous Fe and Ru complexes. (iPr-DAB)Fe(CO)2I2 and (iPr-DAB)FeI2: a perfectly reversible CO-carrier system. (R-DAB=N,N′-R2-1,4-diaza-1,3-butadiene)

  摘要：

  Fe(Pr-i-DAB)(CO)(3) (1a) oxidatively adds I-2 to give (Pr-i-DAB)Fe(CO)(2)-trans-I-2 (Za). Photochemically or thermally, 2a readily dissociates both carbonyl ligands to give tetrahedral Fe(Pr-i-DAB)I-2 (3a). Under an atmosphere of CO, complex 2a is quantitatively regenerated from 3a. The X-ray crystal structures of 2a and 3a have been determined. 2a: triclinic, space group P (1) over bar, a = 8.7624(3). b = 9.0550(4), c = 10.6512(6) Angstrom, alpha = 95,429(4) beta = 105.245(4), gamma = 95.209(3)degrees Z = 2, R = 0.0251. 3a: orthorhombic, space group Aba2, a = 11.2693(10), b = 15.933(2), c = 7.5958(10) A, Z = 4, R = 0.036. Contrasting the behaviour of 2a, the analogous ruthenium complexes (R-DAB)Ru(CO)(2)trans-I-2 (4) are very stable, and the carbonyl ligands cannot be dissociated thermally. In the dichloro complexes. of which both the kinetic trans- (5) and the thermodynamic cis-compounds (6) have been isolated, both isomers undergo a photochemical CO mono-substitution to give for example the isolable trans-dichloro methanol complex (7). (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00162-0
• 作为产物：
  描述：

  dicarbonyldichlororuthenium 、 N,N'-二异丙基乙烷-1,2-二亚胺 以 甲醇 为溶剂， 以16%的产率得到(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)Ru(CO)2(trans-Cl)2
  参考文献：
  名称：

  Comparing structures and reactivity in analogous Fe and Ru complexes. (iPr-DAB)Fe(CO)2I2 and (iPr-DAB)FeI2: a perfectly reversible CO-carrier system. (R-DAB=N,N′-R2-1,4-diaza-1,3-butadiene)

  摘要：

  Fe(Pr-i-DAB)(CO)(3) (1a) oxidatively adds I-2 to give (Pr-i-DAB)Fe(CO)(2)-trans-I-2 (Za). Photochemically or thermally, 2a readily dissociates both carbonyl ligands to give tetrahedral Fe(Pr-i-DAB)I-2 (3a). Under an atmosphere of CO, complex 2a is quantitatively regenerated from 3a. The X-ray crystal structures of 2a and 3a have been determined. 2a: triclinic, space group P (1) over bar, a = 8.7624(3). b = 9.0550(4), c = 10.6512(6) Angstrom, alpha = 95,429(4) beta = 105.245(4), gamma = 95.209(3)degrees Z = 2, R = 0.0251. 3a: orthorhombic, space group Aba2, a = 11.2693(10), b = 15.933(2), c = 7.5958(10) A, Z = 4, R = 0.036. Contrasting the behaviour of 2a, the analogous ruthenium complexes (R-DAB)Ru(CO)(2)trans-I-2 (4) are very stable, and the carbonyl ligands cannot be dissociated thermally. In the dichloro complexes. of which both the kinetic trans- (5) and the thermodynamic cis-compounds (6) have been isolated, both isomers undergo a photochemical CO mono-substitution to give for example the isolable trans-dichloro methanol complex (7). (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00162-0

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
• Synthesis of the monohydride complexes HRu2(X)(CO)5(iPr-NCHCHN-iPr) (X=Cl, I); hydrogenation of the central CC bond of the coordinated α-diimine ligands. X-ray. single crystal structure of HRu2(Cl)(CO)5(iPr-NCHCHN-iPr)
  作者：Marco J.A. Kraakman、Cornelis J. Elsevier、Vincent W. de Haar、Kees Vrieze、Anthony L. Spek

  DOI：10.1016/s0020-1693(00)81652-7

  日期：1993.1

  and bond breaking steps during the hydrogenation process. Reaction of 3a with AgOTF yielded [OTF][HRu 2 (CO) 5 ( i Pr-DAB)] ( 6 ), which subsequently could be converted to [OTF][HRu 2 (CO) 5 (L)( i Pr-DAB)] (LCO ( 8 ); L=′Bu-NC ( 9 )) and to [HRu 2 (X)(CO) 5 ( i Pr-DAB)] (XCo(CO) 4 ( 3d ); XMn(CO) 5 ( 3e ); XCN ( 3f )). Whereas the DAB ligand of 6 could be reduced, complexes 3d-f, 8 and 9 could

  具有一个末端和一个桥联氢化物的H 2 Ru 2（CO）5（i Pr-DAB H，R}）（RH（1a）;RMe（1b））与CX 4的反应（XCl;XI）得到HRu 2（X）（CO）5（i Pr-DAB H，R}）（XCl，RH（3a）; X = CI，R = Me（ 3b）;XI，RH（3c））。如通过单晶X射线结构测定所证实的，配合物3a包含由氢化物和6eσ-N，μ2-N'，η2-CN'键联的DAB配体桥接的双金属单元，而氯化物为末端保税的。3a的晶体是单斜晶体，空间群P 2 1 / c，a = 12.421（2），b = 12.003（2），c = 13.227（1）A，β= 90.22（1）°，Z =4。结构对于2947年观察到的反射，将其精炼为R = 0.043。3a与D 2在70°C的反应得到DRu 2（Cl）（CO）5（i Pr-DAB）（3a'），而3a'可通过与H
• Nanosecond CO Photodissociation and Excited-State Character of [Ru(X)(X′)(CO)₂(<i>N</i>,<i>N</i>′-diisopropyl-1,4-diazabutadiene)] (X = X′ = Cl or I; X = Me, X′ = I; X = SnPh₃, X′ = Cl) Studied by Time-Resolved Infrared Spectroscopy and DFT Calculations
  作者：Anders Gabrielsson、Mike Towrie、Stanislav Záliš、Antonín Vlček

  DOI：10.1021/ic702304k

  日期：2008.5.19

  The character and dynamics of the low-lying excited states of [Ru(X)(X')(CO)(2)(iPr-dab)] (X = X' = Cl or l; X = Me, X' = 1; X = SnPh3, X' = Cl; iPr-dab = N,N'-diisopropyl-1,4-diazabutadiene) were studied experimentally by pico- and nanosecond time-resolved IR spectroscopy (TRIR) and (for X = X' = Cl or l) computationally using density functional theory (DFT) and time-dependent DFT (TD-DFT) techniques. The lowest allowed electronic transition occurs between 390 and 460 nm and involves charge transfer from the Ru(halide)(CO)(2) unit to iPr-dab, denoted (MLCT)-M-1/XLCT (metal-to-ligand/halide-to-ligand charge transfer). The lowest triplet state is well modeled by UKS-DFT-CPCM calculations, which quite accurately reproduce the excited-state IR spectrum in the v(CO) region. It has a (MLCT)-M-3/XLCT character with an intraligand (iPr-dab) (3)pi pi* admixture. TRIR spectra of the lowest triplet excited state show two v(CO) bands that are shifted to higher energies from their corresponding ground-state positions. The magnitude of this upward shift increases as a function of the ligands X and X' [(l)(2) < (Sn)(Cl) < (Me)(l) < (Cl)(2)] and reveals increasing contribution of the Ru(CO)(2) -> dab MLCT character to the excited state. The lowest triplet state of [Ru(Cl)(2)(CO)(2)(iPr-dab)] undergoes a similar to 10 ps relaxation that is followed by CO dissociation, producing cis(CO,CH3CN),trans(Cl,Cl)-[Ru(Cl)(2)(CH3CN)(CO)(iPr-dab)] with a unity quantum yield and 7.2 ns lifetime and without any observable intermediate. To our knowledge, this is the first example of a "slow" CO dissociation from a thermally equilibrated triplet charge-transfer excited state.