(2,3,7,8,12,13,17,18=octaethylporphyrinato)RhI | 69509-36-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: (2,3,7,8,12,13,17,18=octaethylporphyrinato)RhI
• 英文别名: (OEP)RhI；rhodium(III) octaethylporphyrin iodide；Rh(octaethylporphyrinato)I；iodorhodium(III) octaethylporphyrin
• CAS: 69509-36-0
• 化学式: C₃₆H₄₄IN₄Rh
• 分子量: 762.582
• InChiKey: OQTWKRCNDDSZNY-YAJYDHHFSA-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：

  (2,3,7,8,12,13,17,18=octaethylporphyrinato)RhI 在 AgCN 作用下， 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  异氰化物与卟啉铑的反应：甲酰亚胺基和氨基甲酰基复合物的形成以及CN-R键的裂解

  摘要：

  Reactions of alkyl and aryl isocyanides with (octaethylporphyrinato)rhodium hydride, (OEP)Rh-H, (octaethylporphyrinato)rhodium(II) dimer, [(OEP)Rh]2, and (tetramesitylporphyrinato)rhodium(II), (TMP)Rh., have been investigated for comparison with CO reactivity. Alkyl and aryl isocyanides interact with (OEP)Rh-H to form 1:1 adducts, (OEP)Rh(H)(CNR), which react further to produce formimidoyl complexes, (OEP)Rh-CH=NR, in analogy with the reaction of (OEP)Rh-H with CO that produces a formyl complex, (OEP)Rh-CHO. [(OEP)Rh]2 forms 1:1 complexes with isocyanides where the 2,6-dimethylphenyl isocyanide derivative persists at equilibrium, but alkyl isocyanides undergo CN- alkyl bond cleavage to form alkyl, (OEP)Rh-R, and cyanide, (OEP)Rh(CN)(CNR), complexes. No evidence was obtained for bridging isocyanide species analogous to the dimetal ketone RhC(O)Rh and dimetal diketone RhC(0)C(0)Rh complexes observed in reactions of [(OEP)Rh]2 with CO. Carbamoyl complexes, (OEP)Rh-C(O)NHR, are formed in reactions of [(OEP)Rh]2 with CNR and H2O or CO and RNH2. The crystal and molecular structures were determined for (OEP)Rh-C(O)NH(C6H3(CH3)2) which crystallizes in the triclinic space group P1 with unit cell dimensions a = 12.256(3) angstrom, b = 13.234(2) angstrom, c = 15.075(3) angstrom, alpha = 61.79(2)-degrees, beta = 75.89(2)-degrees, gamma = 73.39(l)-degrees, V = 2047.7(7) angstrom3, and Z = 2.

  DOI：

  10.1021/om00033a010
• 作为产物：
  描述：

  Rh(OEP)Ph 在 碘 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 碘苯 、 (2,3,7,8,12,13,17,18=octaethylporphyrinato)RhI
  参考文献：
  名称：

  芳烃碳氢键的活化。铑（III）卟啉具有高度区域选择性的亲电芳族金属化作用，并随后裂解碳-铑键

  摘要：

  DOI：

  10.1021/om00132a030

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。
• Ruthenium(ii) and rhodium(iii) porphyrin phosphine complexes: influence of substitution pattern on structure and electronic properties
  作者：Andrew D. Bond、Jeremy K. M. Sanders、Eugen Stulz

  DOI：10.1039/c1nj20598f

  日期：——

  A series of ruthenium(II) and rhodium(III) porphyrin complexes with diphenyl phenylacetylene phosphine (dpap) was synthesised and fully characterised by UV-vis, 1H NMR and 31P1H} NMR spectroscopy, and in most cases also by single-crystal X-ray diffraction. The substitution pattern of the porphyrin was varied with increasing meso-phenyl substitution, from octa-ethyl porphyrin (OEP), through diphenyl

  一系列钌（II）和铑（III）卟啉配合物二苯基苯乙炔膦合成了（dpap）（dpap），并通过UV-vis，1 H NMR和31 P 1 H} NMR光谱进行了全面表征，在大多数情况下，还通过单晶X射线衍射进行了表征。卟啉的取代模式与递增改变内消旋-苯基取代，从八乙基卟啉 （OEP），通过 二苯基二乙基卟啉 （民进党）， 到 四苯基卟啉（TPP）和3,5-二-吨丁基四苯基卟啉（tbTPP）。dpap可以轻松取代母体Ru（CO）（卟啉）的CO配体和Rh（I）（卟啉）的碘化物，生成双膦配合物M（dpap）2（卟啉）。UV-vis光谱显示，某些配合物在10 -6 M的浓度下会部分解离，并且缔合常数估计在第一个范围为10 6至10 7 M -1，在10 4到10 M范围内。第二次结合事件为10 6 M -1。在1尽管它们在固态中显示出非常相似的几何形状，但它们的1 H NMR化学位移变化很大，并
• 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。
• Synthesis and Reactivity of Porphyrinatorhodium(II)−Triethylphosphine Adducts:  The Role of PEt₃ in Stabilizing a Formal Rh(II) State
  作者：James P. Collman、Roman Boulatov

  DOI：10.1021/ja001364u

  日期：2000.12.1

  Rh(por)H, where por is an octaethyl- or meso-tetraphenylporphyrin dianion,reacts with triethylphosphine to form stable mononuclear paramagnetic formally-Rh-II complexes, Rh(OEP)(PEt3) and Rh(TPP)-(PEt3)(2). The former adduct is also obtained as the sole product of the reaction between Rh-2(OEP)(2) and FEt3. The EPR spectroscopy at 77 K shows both complexes to have mainly porphyrin-based HOMOs. The composition and the reactivity of Rh(TPP.-)(PEt3)(2) support its formulation as Rh-III(TPP'-)(PEt3)(2). In contrast, Rh(OEP)(PEt3)(2) demonstrates the reactivity of both a Rh-II d(7) center and a porphyrin pi -anion radical. The adduct reacts with O-2 as a Rh-II(por) species, originally forming a Rh-III-superoxido derivative. In contrast, with water Rh(OEP)(PEt3) reacts as a porphyrin sz-anion radical, yielding a Rh-III-octaethylphlorin complex. The latter is the first characterized phlorin complex of a heavy transition metal. The dual reactivity of Rh(OEP)(PEt3) is proposed to arise from thermal excitation of the unpaired electron from the porphyrin-based HOMO onto the metal-based LUMO (d sigma*(Rh-P)) Unlike the other reported 1:1 adducts of Rh-II(por) species with sigma -basic ligands, Rh(OEP)(PEt3) is remarkably stable toward disproportionation to Rh-I and Rh-III. To understand the origin of this stability, the affinity of Rh-III(OEP)(+) toward PEt3 and pyridine was measured spectrophotometrically. The high binding affinity of PEt3 to Rh(OEP) is proposed as the underlying cause of the increased stability of Rh(OEP)(PEt3) toward disproportionation.
• Callot, H. J.; Schaeffer, E., Nouveau Journal de Chimie, 1980, vol. 4, p. 311 - 314
  作者：Callot, H. J.、Schaeffer, E.

  DOI：——

  日期：——