octaethylporphyrinatorhodium(II) dimer | 63439-10-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯嗪
• 英文名称: octaethylporphyrinatorhodium(II) dimer
• 英文别名: [(2,3,7,8,12,13,17,18=octaethylporphyrinato)Rh]2
• CAS: 63439-10-1
• 化学式: C₇₂H₈₈N₈Rh₂
• 分子量: 1271.36
• InChiKey: XVUWJFIYGPNEDA-CYJACJFISA-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：

  octaethylporphyrinatorhodium(II) dimer 以 环己烷 为溶剂， 生成 rhodium(II) octaethylporphrin
  参考文献：
  名称：

  Wayland, Bradford B.; Coffin, Virginia L.; Farnos, Maria D., Inorganic Chemistry, 1988, vol. 27, # 15, p. 2745 - 2747

  摘要：

  DOI：
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 octaethylporphyrinatorhodium(II) dimer
  参考文献：
  名称：

  Formation and thermal reactions of rhodium-carbon bonds derived from the reactions of octaethylporphyrin-rhodium(III) dimer with alkyl carbon-hydrogen bonds in alkyl aromatics

  摘要：

  DOI：

  10.1021/ja00312a023
• 作为试剂：
  描述：

  (octaethylporphyrinato)(hydrido)rhodium(II) 在 octaethylporphyrinatorhodium(II) dimer 一氧化碳 作用下， 以 not given 为溶剂， 生成 (octaethylporphyrinato)rhodium(II)*CHO
  参考文献：
  名称：

  铑卟啉配合物的插入和氧化加成反应。新型自由基链机制

  摘要：

  Cinetique des reaction de Rh 2 (OEP) 2 et (OEP)RhH avec le 苯乙烯。反应机制

  DOI：

  10.1021/ja00300a044

文献信息

• Reactions of CH bonds in organica oxygenates with octaethylporphyrinato rhodium(II) and iridium(II) dimers
  作者：Kenneth J. Del Rossi、Xiao-Xiang Zhang、Bradford B. Wayland

  DOI：10.1016/0022-328x(95)05569-b

  日期：1995.11

  Metalloporphyrin dimers, [(OEP)M]2 (), are observed to react with CH bond units in aldehyes, kenotes and benzyl alohols. Aldehydes, R2CHCHO, preferentially react at the alkyl group adjacent to the carbonyl position to yield β-formyl complexes, (OEP)M-CR2CHO, even when reaction of the aldehydic CH unit is thermodynamically favored. Reaction at the carbon-hydrogen bond adjacent to the carbonyl group

  观察到金属卟啉二聚体[（OEP）M] 2（）与醛，酮和苄醇中的CH键单元反应。醛，R 2 CHCHO优先在与羰基位置相邻的烷基上反应，生成β-甲酰基络合物（OEP）M-CR 2 CHO，即使在热力学上有利于醛CH单元的反应。有人提出，通过将金属卟啉加到烯醇异构体中以生成中间体烷基桥连的配合物（OEP）M-CR'（OH）-M（OEP），可以在与羰基相邻的碳氢键上发生反应。随后通过有效的β-OH迁移反应形成（OEP）M-CR 2 C（O）R'和（OEP）MH复合物。[（OEP）Rh] 2也与苄醇C反应6 H 5 CH（OH）R（R = H，CH 3，C（O）C 6 H 5），制得中间体α-氢烷基衍生物（OEP）Rh-CR（OH）C 6 H 5，随后离解得到有机羰基物质，C 6 H [in5] C（O）R和（OEP）Rh-H。
• Reactions of Rhodium Porphyrins with Lactones, Silanes, and Stannanes
  作者：Tadashi Mizutani、Tetsuya Uesaka、Hisanobu Ogoshi

  DOI：10.1021/om00001a049

  日期：1995.1

  (2,3,7,8,12,13,17,18-Octaethylporphyrinato)rhodium(I) (Rh(I)OEP) cleaved the alkyl-oxygen bond of four-membered-ring and five-membered-ring lactones (beta-propiolactone (1), beta-butyrolactone (2), and gamma-butyrolactone (3)) at room temperature to regioselectively yield (omega-carboxyalkyl)Rh(III)OEP. [Rh(II)OEP}(2)] reacted with R(2)(1)R(2)MH (8, M = Si, R(1) = R(2) = Et; 9, M Si, R(1) = R(2) = Ph; 10, M = Si, R(1) = Me, R(2) = Ph; 11, M = Si, R(1) = Me, R(2) = Oet; 16, M = Sn, R(1) = R(2) = Bu; 17, M = Sn, R(1) = R(2) = Ph) to yield Rh-III(MR(2)(1)R(2))OEp. These alkyl-, silyl-, and stannylrhodium complexes of OEP were characterized by H-1, C-13, Si-29, and Sn-119 NMR, IR, UV-vis, and mass spectroscopy. (triethylsilyl)Rh(III)OEP crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 17.14(8) Angstrom, b = 14.94(5) Angstrom, c = 31.22(5) Angstrom, and beta = 103.5(2)degrees; the density is 1.28 g/cm(3) for Z = 8. The porphyrin plane is almost planar, and the rhodium metal resides on the plane. The Rh-Si distance is 2.32(1) A, and dl the eight ethyl groups on the pyrroles are directed toward the triethylsilyl group. The present method has proved to be a facile way to prepare bimetallic rhodium complexes of porphyrin.

  (2,3,7,8,12,13,17,18-辛乙基卟啉酸根)铑(I)（Rh(I)OEP）在室温下裂解四元环和五元环内酯（β-丙内酯（1）、β-丁内酯（2）和γ-丁内酯（3））的烷基氧键，选择性生成（ω-羧基烷基）Rh(III)OEP。[Rh(II)OEP}(2)]与R(2)(1)R(2)MH（8，M=Si，R(1)=R(2)=Et；9，M=Si，R(1)=R(2)=Ph；10，M=Si，R(1)=Me，R(2)=Ph；11，M=Si，R(1)=Me，R(2)=OEt；16，M=Sn，R(1)=R(2)=Bu；17，M=Sn，R(1)=R(2)=Ph）反应，生成Rh-III(MR(2)(1)R(2))OEp。这些OEP的烷基、硅基和锡基铑配合物通过H-1, C-13, Si-29和Sn-119 NMR、IR、UV-Vis和质谱进行了表征。[(三乙基硅基)Rh(III)OEP]在单斜晶系C2/c空间群中结晶，晶胞尺寸为a=17.14(8)Å，b=14.94(5)Å，c=31.22(5)Å，β=103.5(2)度；密度为1.28 g/cm³，Z=8。卟啉平面几乎平坦，铑金属位于平面上。Rh-Si距离为2.32(1)Å，八个吡咯上的乙基均指向三乙基硅基。本方法已被证明是制备卟啉双金属铑配合物的一种简便方法。
• Thermodynamic studies of competitive adduct formation: single- and double-insertion reactions of carbon monoxide with rhodium octaethylporphyrin dimer
  作者：Virginia L. Coffin、W. Brennen、Bradford B. Wayland

  DOI：10.1021/ja00226a022

  日期：1988.8

  for double insertion of CO into the Rh-Rh bond. NMR methods are used to determine enthalpy and entropy changes for the reaction of 1 with CO to form the following: 2, /Delta/H/sub 2//degree/ = /minus/10/plus minus/ 1 kcal/mol (/minus/41 /plus minus/ 4 kJ/mol), /Delta/S/sub 2//degree/ = /minus/26 /plus minus/ 4 cal/K/center dot/mol/minus/109 /plus minus/ 17 J/K/center dot/mol; 3, /Delta/H/sub 3//degree/

  一氧化碳与（八乙基卟啉）铑二聚体 ((OEP)Rh)/sub 2/ 在甲苯中的反应产生和平衡系统，涉及四种物质：((OEP)Rh)/sub 2/ (1), ((OEP) Rh)/sub 2/(CO) (2)、(OEP)RhC(O)Rh(OEP) (3) 和 (OEP)RhC(O)C(C)Rh(OEP) (4)。没有发现形成 1 的二羰基加合物的证据，这是根据金属-金属键合卟啉二聚体所需的结构特征来解释的。/sup 1/H 和 /sup 13/C NMR 证据表明 CO 双插入 Rh-Rh 键。NMR 方法用于确定 1 与 CO 反应的焓变和熵变，形成以下： 2, /Delta/H/sub 2//degree/ = /minus/10/plus minus/ 1 kcal/mol (/减/41 /加减/ 4 kJ/mol), /Delta/S/sub 2//degree/ = /minus/26
• Preparation of heterobimetallic compounds containing octaethylporphyrinrhodium and their reactions with hydrogen and carbon monoxide
  作者：H.William Bosch、Bradford B. Wayland

  DOI：10.1016/s0022-328x(00)99352-5

  日期：1986.12

  Octaethylporphyrinrhodium dimer ([Rh(OEP)]2) reacts with a series of transition metal dimers (M′M′; M′ = Mn(CO)5; Mo(CO)3Cp; Ru(CO)2C5Me5) to form metalmetal bonded heterobimetallic compounds ((OEP)RhM′). The heterobimetallic compounds reported in this paper react with H2 and CO to produce M′H and equilibrium quantities of Rh(OEP)(H) and Rh(OEP)(CHO).

  八乙基卟啉铑二聚体（[Rh（OEP）] 2）与一系列过渡金属二聚体（M'M'; M'= Mn（CO）5 ; Mo（CO）3 Cp; Ru（CO）2 C 5 Me 5）形成金属金属键合的异双金属化合物（（OEP）RhM'）。本文报道的杂双金属化合物与H 2和CO反应生成M'H以及平衡量的Rh（OEP）（H）和Rh（OEP）（CHO）。
• Radical-like reactivity of rhodium(II) octaethylporphyrin dimer with trimethylphosphite
  作者：Bradford B. Wayland、Bruce A. Woods

  DOI：10.1039/c39810000475

  日期：——

  Rhodium(II) octaethylporphyrin dimer, (Rh-OEP)2, reacts with P(OMe)3 to produce RhOEP[P(O)-(OMe)2] and products associated with the methyl radical, indicative of an unusual donor-induced metallo-radical process.

  铑（II）八乙基卟啉二聚体（Rh-OEP）2与P（OMe）3反应生成RhOEP [P（O）-（OMe）2 ]和与甲基相关的产物，表明不正常的供体诱导金属自由基过程。