trans-[(H2O)([14]ane-N4)RhH](2+) | 182117-10-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-[(H2O)([14]ane-N4)RhH](2+)
• 英文别名: trans-[C10H24N4Rh(H2O)H](2+)；trans-[Rh(H2O)H(1,4,8,11-tetraazacyclotetradecane)](2+)；trans-(cyclam)(water)Rh(hydride)(2+)
• CAS: 182117-10-8；182265-49-2；261176-77-6；551951-88-3；551951-91-8
• 化学式: C₁₀H₂₇N₄ORh
• 分子量: 322.256
• InChiKey: DBYMQAMUESNLKI-UHFFFAOYSA-N

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：

  trans-[(H2O)([14]ane-N4)RhH](2+) 以 高氯酸 为溶剂， 生成 trans-[([14]ane-N4)Rh(H2O)](2+)
  参考文献：
  名称：

  Macrocyclic Rhodium(III) Hydrides and a Monomeric Rhodium(II) Complex

  摘要：

  Several mononuclear N-4-macrocyclic Rh(III) hydrides were prepared and characterized in the solid state and in solution. H-1 NMR, IR, and UV data are reported. The complex {trans-(Cl)([14]aneN(4))RhH}(2)(ZnCl4) . dmso (1 . dmso) crystallizes in the triclinic system, space group P (1) over bar, in a unit cell of dimensions a = 10.680(3) Angstrom, b = 13.360(3) Angstrom, c = 14.277(4) Angstrom, alpha = 86.49(2)degrees, beta = 83.18(2)degrees, gamma = 66.64(2)degrees. The data refined to a final value of R = 0.070 and R(w), = 0.13 based on 2687 observed reflections. UV photolysis of chloride-free (H2O)L(1)RhH(2+) results in homolytic Rh-H bond cleavage. The rhodium(II) product, L(1)Rh(H2O)(2+), was characterized by ESR and UV spectroscopies. This species survives in acidic aqueous solution for over half an hour at room temperature. The photolysis of (H2O)L(1)RhH(2+) in the presence of O-2 produces the superoxorhodium(III) ion, trans-L(1)RhOO(2+).

  DOI：

  10.1021/ic960300a
• 作为产物：
  描述：

  [trans-(Cl)([14]ane-N4)RhH]2(ZnCl4) 、 水 以 高氯酸 为溶剂， 生成 trans-[(H2O)([14]ane-N4)RhH](2+)
  参考文献：
  名称：

  Macrocyclic Rhodium(III) Hydrides and a Monomeric Rhodium(II) Complex

  摘要：

  Several mononuclear N-4-macrocyclic Rh(III) hydrides were prepared and characterized in the solid state and in solution. H-1 NMR, IR, and UV data are reported. The complex {trans-(Cl)([14]aneN(4))RhH}(2)(ZnCl4) . dmso (1 . dmso) crystallizes in the triclinic system, space group P (1) over bar, in a unit cell of dimensions a = 10.680(3) Angstrom, b = 13.360(3) Angstrom, c = 14.277(4) Angstrom, alpha = 86.49(2)degrees, beta = 83.18(2)degrees, gamma = 66.64(2)degrees. The data refined to a final value of R = 0.070 and R(w), = 0.13 based on 2687 observed reflections. UV photolysis of chloride-free (H2O)L(1)RhH(2+) results in homolytic Rh-H bond cleavage. The rhodium(II) product, L(1)Rh(H2O)(2+), was characterized by ESR and UV spectroscopies. This species survives in acidic aqueous solution for over half an hour at room temperature. The photolysis of (H2O)L(1)RhH(2+) in the presence of O-2 produces the superoxorhodium(III) ion, trans-L(1)RhOO(2+).

  DOI：

  10.1021/ic960300a

文献信息

• Kinetics and Thermodynamics of Hydrogen Atom Transfer to Superoxometal Complexes
  作者：Andreja Bakac

  DOI：10.1021/ja971987g

  日期：1997.11.1

  Dicationic metal superoxo complexes, L(H2O)MOO2+ (M = Rh, Cr; L = (NH3)4, (H2O)5, [14]aneN4) react with rhodium hydrides L‘(H2O)RhH2+ (L‘ = (NH3)4, [14]aneN4, and meso-Me6-[14]aneN4) to yield L(H2O)MOOH2+ and L‘(H2O)2Rh2+. The rhodium(II) product is rapidly converted to L‘(H2O)RhOO2+ in a reaction with molecular oxygen (k ∼ 108 M-1 s-1), or to a binuclear superoxo product in the absence of O2. When

  双阳离子金属超氧配合物，L(H2O)MOO2+ (M = Rh, Cr; L = (NH3)4, ( )5, [14]aneN4) 与氢化铑反应 L'( )RhH2+ (L' = (NH3) )4、[14]aneN4 和内消旋-Me6-[14]aneN4) 生成 L( )MOOH2+ 和 L'( )2Rh2+。铑 (II) 产物在与分子氧 (k ∼ 108 M-1 s-1) 反应中迅速转化为 L'( )RhOO2+，或在没有 O2 的情况下转化为双核超氧产物。当两个反应物中的中心金属原子和非参与配体相同时（M = Rh，L = L'），O2 插入 Rh-H 键变为催化性，L'RhH2+ + O2 → L'RhOOH2+（L'RhOO2+ =催化剂）。氢转移步骤表现出很大的动力学同位素效应（对于 CraqOO2+ 与 ([14]aneN4)( )RhH2+ 的反应，kH/kD
• Base-Catalyzed Insertion of Dioxygen into Rhodium−Hydrogen Bonds: Kinetics and Mechanism
  作者：Ewa Szajna-Fuller、Andreja Bakac

  DOI：10.1021/ic901808t

  日期：2010.2.1

  heterolytic cleavage of the Rh−H bond and formation of a reactive Rh(I) intermediate. A competition between O2 and H2O for Rh(I) is the source of the observed dependence on O2. In support of this mechanism, there is a significant kinetic isotope effect for the initial step, L1(OH(D))RhH(D)+ + OH(D)− L1(OH(D))RhI + H(D)2O, k1H/k1D = 1.7, and k−1H/k−1D = 3.0. The activation parameters for k1 for trans-L1(OH)RhH+

  分子氧和铑的氢化物L（OH）RhH的之间的反应+（L =（NH 3）4，反式-L 1，和顺式-L 1，其中L 1 = cyclam）在碱性水溶液中迅速产生相应氢过络合物。在pH范围8
• Kinetics and mechanism of the reduction of a macrocyclic Rh(iii) complex by chromium(ii) ions: pH-controlled selectivity to rhodium(ii) vs. rhodium(iii) hydride
  作者：Ewa Szajna-Fuller、Andreja Bakac

  DOI：10.1039/c1dt10747j

  日期：——

  Aqueous chromium(II) ions reduce a macrocyclic Rh(III) complex L1(H2O)2Rh3+ (L1 = 1,4,8,11-tetraazacyclotetradecane) to the hydride L1(H2O)RhH2+ in two discrete, one-electron steps. The first step generates L1(H2O)Rh2+ with kinetics that are first order in each rhodium(III) complex and Cr(H2O)62+, and inverse in [H+], k/M−1s−1 = 0.065/(0.0031 + [H+]). Further reduction of L1(H2O)Rh2+ to L1(H2O)RhH2+

  铬（II）水溶液还原大环Rh（III）络合物L 1（H 2 O）2 Rh 3+（L 1 =1,4,8,11-四氮杂环十四烷）在两个离散的单电子步骤中生成氢化物L 1（H 2 O）RhH 2+。所述第一步骤产生大号1（H 2 O）的Rh 2+与在每个铑（一级动力学III）配合物和Cr（H 2 O）6 2+，和在逆[H + ]，ķ / M - 1 s -1 = 0.065 /（0.0031 + [H + ]）。L 1（H 2 O）Rh 2+进一步还原为L 1（H 2 O）RhH 2+在动力学上独立于[H + ]，k / M -1 s -1 = 0.30。[H + ]依赖性的差异使得可以控制两个步骤的相对速率，以生成L 1（H 2 O）Rh 2+或L 1（H 2 O）RhH 2+作为最终产物。
• Hydrogen Atom and Hydride Transfer in the Reactions of Chromium(IV) and Chromium(V) Complexes with Rhodium Hydrides. Crystal Structure of a Superoxorhodium(III) Product
  作者：Andreja Bakac、Ilia A. Guzei

  DOI：10.1021/ic991098p

  日期：2000.2.1

  s(-1); (NH3)4, 2,500; L2, 1,000) and isotope effects (L = L1, kie = 5.4; L2, 6.2). The superoxo complex [L1(CH3CN)RhOO](CF3SO3)2.H2O crystallizes with discrete anions, cations, and solvate water molecules in the lattice. All moieties are linked by a network of hydrogen bonds of nine different types. The complex crystallized in the triclinic space group P1 with a = 9.4257(5) A, b = 13.4119(7) A, c = 13

  在分子氧存在下，水溶液中的铬酸根离子Cr（IV）aqO2 +与氢化物L（H2O）RhH2 +（L = L1 = [14] aneN4和L2 = meso-Me6- [14] aneN4）反应，生成生成Cr（aq）3+和超氧配合物L（ ）RhOO2 +。在25摄氏度时，速率常数约为10（4）M（-1）s（-1）（L = L1）和1.12 x 10（3）M（-1）s（-1）（L = L2 ）。两种反应均显示出适度的氘同位素效应，kRhH / kRhD =约3（L1）和3.3（L2），但无溶剂同位素效应，k / kD2O =1。提出的机理涉及氢原子的提取，然后捕获LRh（ ）2+与分子氧。没有证据表明在L（ ）RhH2 +和（salen）CrVO +之间的反应中会形成L（ ）Rh2 +。建议的氢化物转移由速率常数的大小（L = L1，k = 8,800 M（-1）s（-1）;（NH3）4，2，500;