Ir(triphos)(η(3)-2-vinylthiophenolate) | 156701-47-2

• 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: Ir(triphos)(η(3)-2-vinylthiophenolate)
• 英文别名: [3-diphenylphosphanyl-2-(diphenylphosphanylmethyl)-2-methylpropyl]-diphenylphosphane;2-ethenylbenzenethiolate;iridium(1+)
• CAS: 156701-47-2
• 化学式: C₄₉H₄₆IrP₃S
• 分子量: 952.112
• InChiKey: VYIAIAIJMLTJTD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四氟硼酸-二乙醚络合物 、 Ir(triphos)(η(3)-2-vinylthiophenolate) 以 四氢呋喃 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  HDS Model Systems. Coordination, Opening, and Hydrogenation of Benzo[b]thiophene at Iridium

  摘要：

  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)IrH{mu-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)IrH{mu-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.

  DOI：

  10.1021/ja00089a027
• 作为产物：
  描述：

  (CH₃C(CH₂P(C₆H₅)2)3)Ir(H)(CHCHC₆H₄S) 以 四氢呋喃 为溶剂， 以85%的产率得到Ir(triphos)(η(3)-2-vinylthiophenolate)
  参考文献：
  名称：

  HDS Model Systems. Coordination, Opening, and Hydrogenation of Benzo[b]thiophene at Iridium

  摘要：

  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)IrH{mu-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)IrH{mu-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.

  DOI：

  10.1021/ja00089a027

文献信息

• CH bond activation of thiophenes at iridium: a lower energy process than CS bond scission
  作者：Claudio Bianchini、M. Victoria Jiménez、Andrea Meli、Simonetta Moneti、Francesco Vizza

  DOI：10.1016/0022-328x(95)05606-p

  日期：1995.11

  reacts with thiophene (T) or benzo[b]thiophene (BT) to give, in the temperature range from 67 to 100°C, mixtures of CH and CS insertion product as a result of parallel reactions [triphos = MeC(CH2PPh2)3]. Above 100°C, the (thienyl)dihydride complexes convert to the thermodynamically more stable CS insertion products (butadienethiolate and 2-vinylthiophenolate complexes) through an intramolecular

  由（triphos）Ir（H）2（C 2 H 5）在THF中热解原位生成的16电子片段[（triphos）IrH]与噻吩（T）或苯并[ b ]噻吩（BT）反应通过平行反应[triphos = MeC（CH 2 PPh 2）3 ] ，可在67至100°C的温度范围内得到C 67H和CS插入产物的混合物。高于100°C，（噻吩基）二氢化物配合物通过不涉及T或BT的分子内机理转化为热力学上更稳定的CS插入产物（丁二烯硫醇盐和2-乙烯基硫酚盐复合物）离解。将其与二苯并噻吩的类似反应进行比较。
• Bianchini, Claudio; Casares, Juan A.; Jiménez, M. Victoria, Organometallics, 1995, vol. 14, # 10, p. 4850 - 4857
  作者：Bianchini, Claudio、Casares, Juan A.、Jiménez, M. Victoria、Meli, Andrea、Moneti, Simonetta、Vizza, Francesco、Herrera, Verónica、Sánchez-Delgado, Roberto

  DOI：——

  日期：——