bis(ethylene)pentamethylcyclopentadienyl iridium

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: bis(ethylene)pentamethylcyclopentadienyl iridium
• 英文别名: (η(5)-C5Me5)Ir(η(2)-C2H4)2；(η5-C5Me5)Ir(C2H4)2
• 化学式: C₁₄H₂₃Ir
• 分子量: 383.557
• InChiKey: PTCDSXUUSKNNBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(ethylene)pentamethylcyclopentadienyl iridium 、 三甲基锡 以 环己烷 为溶剂， 生成 (η-pentamethylcyclopentadienyl)dihydridobis(trimethyltin)iridium(V)
  参考文献：
  名称：

  二氢双（三烷基锡）（五甲基环戊二烯基）-铑（V）和铱（V）配合物的合成，表征及相关反应

  摘要：

  通过R 3 SnH和[（C 5 Me 5 M ）的反应制备二氢双（三烷基锡烷基）-铑（V）和-铱（V）络合物[C 5 -Me 5 M（H）2（SnR 3）2 ]。）2 Cl 4 ]或[C 5 Me 5 M（C 2 H 4）2 ]。光谱上将最后反应中的中间体鉴定为[C 5 Me 5 M（H）（SnR 3）（C 2 H 4）]（MIr，RMe），但无法检测到铑类似物。通过R 3 SnH与[C 5 Me 5 M（CO）2 ]的反应容易获得氢化羰基配合物[C 5 Me 5 M（H）-（SnR 3）（CO）]。它们比其甲硅烷基类似物更稳定，但铑络合物缓慢分解。配合物[C 5 Me 5 M（H）2（SnR 3）2 ]非常耐亲核试剂的攻击，但铑配合物与PPh 3缓慢反应，生成[C 5 Me 5 Rh（PPh 3））（SnR 3）2 ]; 此行为与[C 5 Me 5 Rh（H）2（SiR 3）2 ]所

  DOI：

  10.1016/0022-328x(87)80405-9
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 hexaethyldialuminum 以 苯 为溶剂， 以21%的产率得到bis(ethylene)pentamethylcyclopentadienyl iridium
  参考文献：
  名称：

  Approaches to ethyl(pentamethylcyclopentadienyl)-rhodium or -iridium complexes

  摘要：

  DOI：

  10.1016/s0022-328x(00)98607-8

文献信息

• First example of cyclodimerisation of a phospha-alkyne to a 1,3-diphosphacyclobutadiene. Syntheses of complexes of the type [M(η⁵-C₅R₅){η⁴-(Bu^tCP)₂}] R = H or Me; M = Co, Rh, or Ir): crystal and molecular structure of η⁵-pentamethylcyclopentadienyl-2,4-di-t-butyl-1,3-diphosphacyclobutadienecobalt(<scp>I</scp>), [Co(η⁵-C₅Me₅){η⁴-(Bu^tCP)₂}]
  作者：Peter B. Hitchcock、Mohd Jamil Maah、John F. Nixon

  DOI：10.1039/c39860000737

  日期：——

  Displacement of ethylene from [M(η5-C5R5)(C2H4)2], (R = H, M = Co or Rh; R = Me, M = Co, Rh, or Ir) by treatment with ButCP affords complexes containing the novel 2,4-di-t-butyl-1,3-diphosphacyclobutadiene ring.

  用 ButCP 处理[M(δ-5-C5R5)(C2H4)2]（R = H，M = Co 或 Rh；R = Me，M = Co、Rh 或 Ir），使乙烯从[M(δ-5-C5R5)(C2H4)2]中置换出来，得到含有新型 2,4-二叔丁基-1,3-二磷环丁二烯环的复合物。
• A dinuclear iridium aryldiazenide complex with a η²-η²-N,N′ bridge. Synthesis of [(C₅Me₅)₂Ir₂(CO)₂(µ²-η²-NNC₆H₄OMe)][BF₄] from [(C₅Me₅)Ir(C₂H₄)(N₂C₆H₄OMe)][BF₄]
  作者：Frederick W. B. Einstein、Xiaoqian Yan、Derek Sutton

  DOI：10.1039/c39900001466

  日期：——

  [(C5Me5)Ir(C2H4)(p-N2C6H4OMe)][BF4], 2 and the nitrosyl analogue [(C5Me5)Ir(C2H4)(NO)][BF4], 3 have been synthesized from (C5Me5)Ir(C2H4)2, 1 and [p-N2C6H4OMe][BF4] or [NO][BF4]; 2 reacts with (C5Me5)Ir(CO)2 to give the title dinuclear complex, 4 in which the aryldiazenide ligand bridges in the four-membered dimetalladiaza-ring fashion.

  [(C5Me5)Ir(C2H4)(p-N2C6H4OMe)][BF4]、2和亚硝基类似物[(C5Me5)Ir(C2H4)(NO)][BF4]、3由(C5Me5)Ir(C2H4)2、1和[p-N2C6H4OMe][BF4]或[NO][BF4]合成；2与(C5Me5)Ir(CO)2反应生成标题所示的双核配合物4，其中芳基偶氮配体以四元二金属偶氮环的形式桥联。
• Ruiz, Jose; Bentz, Peter O.; Mann, Brian E., Journal of the Chemical Society, Dalton Transactions, 1987, p. 2709 - 2714
  作者：Ruiz, Jose、Bentz, Peter O.、Mann, Brian E.、Spencer, Catriona M.、Taylor, Brian F.、Maitlis, Peter M.

  DOI：——

  日期：——
• Nixon, John F., Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 471 - 474
  作者：Nixon, John F.

  DOI：——

  日期：——
• Design and Study of Rh(III) Catalysts for the Selective Tail-to-Tail Dimerization of Methyl Acrylate
  作者：Elisabeth Hauptman、Sylviane Sabo-Etienne、Peter S. White、Maurice Brookhart、J. Michael Garner、Paul J. Fagan、Joseph C. Calabrese

  DOI：10.1021/ja00097a011

  日期：1994.9

  The development of an efficient, highly selective Rh(III) catalyst system for the tail-to-tail dimerization of methyl acrylate (MA) to dimethyl hexenedioates, precursors to adipic acid, is described. The catalytic cycle is entered by protonation of Cp*Rh(C2H4)(2)l(Cp* = C(5)Me(5)) to yield Cp*Rh(C2H4) (CH2CH2-mu-H)(+) (7) followed by reaction with methylacrylate. The catalyst resting state has been generated by low-temperature protonation of Cp*Rh(CH2CHCO2-CH3)(2)l (15) and identified as Cp*Rd(CH(2)CH(2)COOMe)(eta(2)-CH(2)CHCO(2)Me)(+) (8) by H-1 and C-13 NMR spectroscopy. Investigation of iridium analogs has led to the isolation and X-ray structural characterization of Cp*Ir(CH(2)CH(2)COOMe)(eta(2)-CH(2)CHCO(2)Me)(+) (23a), in which the orientation of the acrylate ligands is that required for tail-to-tail coupling. At -23 degrees C, complex 8 undergoes beta-migratory insertion to give Cp*RhCH(CH(2)COOMe)(CH2-CH(2)COOMe)(+) (10). Complex 10 was independently synthesized by treatment of complex 7 with trans-MeO(2)CCH=CHCH(2)CH(2)CO(2)Me and was characterized by X-ray crystallography. The free energy of activation for the migration reaction is 18.7 kcal/mol and matches that based on the catalytic turnover (TO) frequency (6.6 TO/min at 25 degrees C, Delta G* = 19 kcal/mol).This observation confirms 8 as the resting state and the C-C coupling reaction as the turnover-limiting step. The catalyst deactivates by formal loss of Hz from complex 10 to produce Cp*Rh(eta(3)-CH3OCOCH2CHCHCHCO2CH3)(+) (9). The structure of complex 9 was verified by an X-ray crystallographic study. Exposure of 9 to an atmosphere of H-2 in the presence of MA regenerates the resting state 8, and dimerization proceeds. Second generation catalysts with increased activity and lifetimes have been developed by replacing the C(5)Me(5) ligand by methylated indenyl ligands. Using the catalytic system derived from (1,2,3-trimethylindenyl)Rh(C2H4>(2) (11), conversion of 54 000 equiv of methyl acrylate to dimethyl hexenedioates could be achieved after 68 h at 55 OC under N-2. Details of the mechanism have been elucidated and resemble closely those of the Cp* system. Similar intermediates to 8 and 10 have been characterized by H-1 and C-13 NMR spectroscopy. In contrast, treatment with methyl acrylate of the more electrophilic systems derived from CpRh(C2H4)(2) (25) (Cp = C5H5) and Cp*Rh(C2H4)(2) (30) (Cp* = C-5(CH3)(4)CF3) results in slow dimerization. Low-temperature protonation of CpRh(CH2CHCO2CH3)(2) (27) with H(Et(2)O)(2)BAr'(4) yields a mixture of rhodium species which upon warming to 23 degrees C converge to the bis-chelate complex CpRhCH(CH(2)COOMe)(CH(2)CH(2)COOMe)(+) (28). Exposure of complex 28 to MA generates the unusual bridged species CpRh(CH2CHCOOCH3)H(CH2CHCOOCH3)(+) (29), which serves as the resting state during dimerization. Treatment of complex 30 with H(Et(2)O)(2)BAr'(4) yields Cp*Rh(C2H4)(CH2CH2-mu-H)(+) (31), which upon reaction with MA clearly produces Cp*RhCH(CH(2)COOMe)(CH(2)CH(2)COOMe)(+) (33), and dimerization proceeds. Finally, attempts to catalyze the dimerization of other functionalized olefins including methyl vinyl ketone, methyl crotonate, 2-vinylpyridine, and 1-vinyl-2-pyrrolidinone are presented.