[(1,1,1-tris(diphenylphosphinomethyl)ethane)Ir(H)2(THF)]BPh4 | 142928-68-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(1,1,1-tris(diphenylphosphinomethyl)ethane)Ir(H)2(THF)]BPh4
• CAS: 142928-68-5
• 化学式: C₂₄H₂₀B*C₄₅H₄₉IrOP₃
• 分子量: 1210.26
• InChiKey: YUGPUCSNNBMBNB-UHFFFAOYSA-N

计算性质

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• sp3杂化的碳原子比例：
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反应信息

• 作为反应物：
  描述：

  2,3-二氢苯并[b]噻吩 、 [(1,1,1-tris(diphenylphosphinomethyl)ethane)Ir(H)2(THF)]BPh4 以 四氢呋喃 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  First example of opening and hydrogenation of 2,3-dihydrobenzo[b]thiophene to 2-ethylthiophenol assisted by a soluble metal complex

  摘要：

  在[(triphos)Ir(H)2(THF)]BPh4中，通过二氢苯[b]硫烯(DHBT)取代THF，生成η1-S-DHBT加合物[(triphos)Ir(H)2(η1-DHBT)]BPh4，该加合物在室温下与KOBut反应，生成中性2-乙烯基硫苯酸衍生物(triphos)Ir(H)2{η1-o-S(C6H4)CHCH2}，同时伴随C2–S键断裂；后者化合物在温和条件下（2巴H2，80 °C）氢化生成2-乙基硫苯酸衍生物(triphos)Ir(H)2{o-S(C6H4)Et}，在严苛条件下（30巴H2，160 °C）氢化生成游离的2-乙基硫苯和(triphos)IrH3。

  DOI：

  10.1039/a900959k
• 作为产物：
  描述：

  四氢呋喃 、 [(1,1,1-tris(diphenylphosphinomethyl)ethane)Ir(H2)(H)2]BPh4 以 四氢呋喃 为溶剂， 生成 [(1,1,1-tris(diphenylphosphinomethyl)ethane)Ir(H)2(THF)]BPh4
  参考文献：
  名称：

  Bianchini, Claudio; Moneti, Simonetta; Peruzzini, Maurizio, Inorganic Chemistry, 1997, vol. 36, # 25, p. 5818 - 5825

  摘要：

  DOI：

文献信息

• Mechanistic Study of Ir(H)2-Assisted Transformations of Ethyne: Cyclotrimerization, Cooligomerization with Ethene, and Reductive Coupling
  作者：Claudio Bianchini、Kenneth G. Caulton、Todd J. Johnson、Andrea Meli、Maurizio Peruzzini、Francesco Vizza

  DOI：10.1021/om00002a046

  日期：1995.2

  The (ethene)dihydride complex [(triphos)Ir(H)(2)(C2H4)]BPh(4) (1) is capable of promoting a variety of transformations of ethyne, including cyclotrimerization to benzene, cooligomerization with ethene to hexa-1,3,5-triene, reductive coupling to buta-1,3-diene, and hydrogenation to ethene (triphos = MeC(CH(2)PPh(2))(3)). A detailed study under various experimental conditions, the detection of several intermediates along the various reaction paths, and the use of isolated complexes in independent reactions, taken together, permit mechanistic conclusions that account for the varied products. In particular, the cyclotrimerization and cooligomerization reactions are mediated by an iridacyclopentadiene species which is trapped by either ethyne or ethene. Consumption of the hydride ligands of 1 by C2H2 or C2H4 is an ingredient for both cyclotrimerization and cooligomerization reactions but is not. necessary to accomplish the reductive dimerization of ethyne to buta-1,3-diene for which, conversely, the two hydride ligands are mandatory.
• Molecular Solid-Gas Organometallic Chemistry. Catalytic and Stoichiometric Iridium-Assisted C-C Bond-Forming Reactions Involving Ethyne and Ethene
  作者：Claudio Bianchini、Mauro Graziani、Jan Kaspar、Andrea Meli、Francesco Vizza

  DOI：10.1021/om00016a020

  日期：1994.4

  Treatment of crystals of the (eta2-ethene)dihydride complex [(triphos)Ir(H)2(C2H4)]BPh4 (1; triphos = MeC(CH2PPh2)3) with ethyne (4 atm) at 70-degrees-C for 3 h results in evolution of ethene and but-2-ene and formation of five different organometallic products, namely the eta4-benzene complex [(triphos)Ir(eta4-C6H6)]BPh4 (2), the eta4-buta-1,3-diene complex [(triphos)Ir(eta4-C4H6)]BPh4 (3), the eta4-cyclohexa-1,3-diene complex [(triphos)Ir(eta4-C6H8)]BPh4 (4), and the crotyl hydride isomers [(triphos)Ir(H) (eta3-MeC3H4)]BPh4 (5-anti and 5-syn) in a kinetic product ratio of 35:5:23:28:9. At 100-degrees-C, the solid-gas reaction produces catalytic amounts of benzene, the catalyst precursor being the eta4-benzene complex 2. Temperature-programmed reactions carried out in a flow reactor and the use of isolated complexes in independent solid-gas reactions permit mechanistic conclusions which account for the varied organic and organometallic products. The ethene ligand in 1 is an essential ingredient for both cyclotrimerization and cooligomerization reactions of ethyne, which are traversed by eta3-crotyl complexes. Conversely, the ethene ligand is a competitive inhibitor for the reductive dimerization of ethyne to buta-1,3-diene, for which the two hydride ligands are mandatory. Comparison with fluid solution-phase systems provides evidence for the control exerted by the constraining environment of the crystal lattice on the solid-gas reactions.
• HDS Model Systems. Coordination, Opening, and Hydrogenation of Benzo[b]thiophene at Iridium
  作者：Claudio Bianchini、Andrea Meli、Maurizio Peruzzini、Francesco Vizza、Simonetta Moneti、Veronica Herrera、Roberto A. Sanchez-Delgado

  DOI：10.1021/ja00089a027

  日期：1994.5

  The eta 4-benzene complexes [(triphos)Ir(C6H6)]Y (Y = BPh(4), 1a; PF6, 1b) react with benzo[b]thiophene (BT) at room temperature to give the unprecedented [(triphos)Ir(eta(3)-C,C,S-C8H6S)]Y (Y = BPh(4), 2a; PF6, 2b) in which intact BT is coordinated to the metal center through the S atom and the C-2=C-3 bond. 2a and 2b are transformed upon mild thermolysis into the iridabenzothiabenzene complexes [(triphos)Ir(eta(2)-C,S-C8H6S)]Y (Y = BPh(4), 3a; PF6, 3b). An X-ray analysis has been carried out on 3a.1.5THF.0.5EtOH. The coordination geometry around iridium may be described as a distorted trigonal-bipyramid, the metal center being surrounded by the three phosphorus atoms of triphos and by a carbon and a sulfur atom from a CS-cleaved BT molecule. Crystal data: triclinic, space group P (1) over bar, a 17.391(3) Angstrom, b = 16.957(4) Angstrom, c = 12.795(3) Angstrom, alpha = 77.51(2)degrees, beta = 80.98(2)degrees, gamma = 75.50(2)degrees, Z = 2, d(calcd) = 1.31 g cm(-3), n(obsd) = 7636, R = 0.072. Interaction of 2a with CO (1 atm, 20 degrees C) yields [(triphos)Ir(CO)(2)]BPh(4) (4) plus free BT, whereas 3a requires more drastic conditions (5 atm, 70 degrees C) to eliminate BT and produce 4. 2a also reacts with H-2 (1 atm, 20 degrees C) to produce [(triphos)Ir(H)(2)(eta(1)-S-BT)]BPh(4) (5), which can be independently prepared by treatment of [(triphos)Ir(H)(2)(THF)]BPh(4) with BT; at 5 atm H-2, free BT is obtained together with [(triphos)Ir(H)(3)], BPh(3), and benzene, as a result of a heterolytic splitting of H-2 at the [(triphos)Ir(H)(2)](+) fragment assisted by the BPh(4)(-), counteranion. The C-S-cleaved BT in 3a is readily hydrogenated (5 atm, 20 degrees C) to 2-ethylbenzenethiolate, producing [(triphos)Ir(H)(2)o-S-(C6H4)C2H5}] (8) plus BPh(3) and benzene also via heterolytic splitting of H-2 assisted by BPh(4)(-), protonolysis of 8 with 2 equiv HCl produces (triphos)IrCl3 with concomitant liberation of 2-ethylbenzenethiol, a primary product of BT HDS. If the PF6- analogue 3b is used instead, the reaction with H-2 under identical conditions yields the thiolate-bridged dimer [(triphos)IrHmu-o-S(C6H4)C2H5}2HIr(triphos)](PF6)(2) (9b). 3a also reacts with LiHBEt(3) to give [(triphos)Ir(H)(eta(2)-C,S-C8H6S)] (11), which converts in THF solution at 66 degrees C into [(triphos)Ir(eta(3)-S(C6H4)CH=CH2)] (12) by hydride migration to C-2; neither 11 nor 12 react with H-2 under mild conditions. Addition of HBF4.OEt(2) to 12 yields [(triphos)Ir(eta(4)-S(C6H4)C(H)Me)]BF4 (13c), which does react with H-2 even at 1 atm to give the thiolate-bridged dimer [(triphos)IrHmu-o-S(C6H4)C2H5}2HIr(triphos)](BF4)(2) (9c). 13c also reacts with H- to give [(triphos)IrH(eta(2)-S(C6H4)C(H)Me)] (14), which in turn reacts with H-2 and HBF4.OEt(2) to yield 8 and 9c, respectively.
• Bianchini, Claudio; Caulton, Kenneth G.; Foltng, Kirsten, Journal of the American Chemical Society, 1992, vol. 114, # 18, p. 7290 - 7291
  作者：Bianchini, Claudio、Caulton, Kenneth G.、Foltng, Kirsten、Meli, Andrea、Peruzzini, Maurizio、Polo, Alfonso、Vizza, Francesco

  DOI：——

  日期：——
• Hydrodesulfurization (HDS) Model Systems. Opening, Hydrogenation, and Hydrodesulfurization of Dibenzothiophene (DBT) at Iridium. First Case of Catalytic HDS of DBT in Homogeneous Phase
  作者：Claudio Bianchini、M. Victoria Jimenez、Andrea Meli、Simonetta Moneti、Francesco Vizza、Veronica Herrera、Roberto A. Sanchez-Delgado

  DOI：10.1021/om00005a035

  日期：1995.5

  The kinetic selectivity for C-H vs C-S activation of dibenzothiophene (DBT) by the [(triphos)IrH] fragment has been observed upon either thermolysis of(triphos)Ir(H)(2)(C2H5) in THF in the temperature range from 70 to 160 degrees C or dehydrohalogenation of (triphos)Ir(H)(2)Cl with t-BuLi at room temperature [triphos = MeC(CH(2)PPh(2))(3)]. C-H bond cleavage already occurs at 20 degrees C to give as many as three isomeric DBTyl complexes of the formula (triphos)Ir(H)(2)(DBTyl). The kinetic preference follows the order 3-DBTyl > 4-DBTyl greater than or equal to 2-DBTyl, while the thermodynamic stability is in the order 4-DBTyl > 3-DBTyl > 2-DBTyl. Both C-H insertion and C-S insertion occur in the temperature range from 120 to 160 degrees C. Above the latter temperature, C-S insertion prevails over C-H insertion, and the complex (triphos)IrH(eta(2)-C,S-DBT) (5) is generated quantitatively. By reaction with H-2 (THF, 170 degrees C, 30 atm of H-2, 4 h), 5 is converted to a 31:69 mixture of the 2-phenylthiophenolate dihydride (triphos)Ir(H)(2)(SC12H9) (7) and the trihydride (triphos)Ir(H)(3) (8) while free 2-phenylthiophenol, DBT, and biphenyl + H2S are evolved in a relative ratio of 48:42:10. In the presence of an excess of DBT, the reaction is catalytic and converts 10 mol of DBT/mol of 5 in 24 h to both hydrogenation (60%) and desulfurization (40%) products. A rationale of the catalysis cycle is discussed in the light of the results of a study involving the use of isolated compounds in a variety of independent reactions. In accord with previous studies, the thiolate complex 7 is proposed as the intermediate species that undergoes desulfurization by action of H-2.