(triphos)Rh(CO)(2-ethylthiophenolate) | 168643-24-1

• 英文名称: (triphos)Rh(CO)(2-ethylthiophenolate)
• 英文别名: (triphos)Rh(CO)[o-S(C6H4)C2H5]
• CAS: 168643-24-1
• 化学式: C₅₀H₄₈OP₃RhS
• 分子量: 892.823
• InChiKey: NWJXHMAGAZNUCG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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反应信息

• 作为产物：
  描述：

  [(triphos)Rh[η2-o-S(C6H4)C2H5]]2 、 一氧化碳 以 二氯甲烷-D2 为溶剂， 生成 (triphos)Rh(CO)(2-ethylthiophenolate)
  参考文献：
  名称：

  The Catalytic Transformation of Benzo[b]thiophene to 2-Ethylthiophenol by a Soluble Rhodium Complex: The Reaction Mechanism Involves Ring Opening Prior to Hydrogenation

  摘要：

  The thermally generated 16-electron fragment [(triphos)RhH] reacts with benzo[b]thiophene (BT) by C-S bond scission to ultimately yield the 2-vinylthiophenolate complex (triphos)Rh[eta(3)-S(C6H4)CH=CH2] (1), which is an efficient catalyst precursor for the hydrogenation of BT into 2-ethylthiophenol (ETSH) and, to a lesser extent, into 2,3-dihydrobenzo[b]thiophene (DHBT) at 160 degrees C and 30 atm H-2 [triphos = MeC(CH(2)PPh(2))(3)]. The mechanism of this unusual catalytic transformation has been established by high pressure NMR spectroscopic (HPNMR) studies combined with the isolation and characterization of key species related to the catalysis. Under catalytic conditions 1 was shown by HPNMR to be completely transformed into (triphos)Rh(H)(2)[o-S(C6H4)C2H5] (2) and [(eta(2)-triphos)Rh{mu-o-S(C6H4)C2H5}](2) (3); removal of H-2 in the presence of ETSH leads to the quantitative formation of (triphos)RhH[o-S(C6H4)C2H5](2) (4), which is also the terminal state of the catalytic system in all experiments carried out in a high pressure reactor under various reaction conditions. The dimer 3 was prepared in a pure form by reaction of (triphos)RhH3 with 1 equiv of ETSH in THF and reacted with excess ETSH to produce 4, with H-2 to give 2, and with CO to yield (triphos)RhH(CO)[o-S(C6H4)C2H5] (6) Conversely, 3 could be obtained by thermally induced reduction elimination of H-2 from 2 even under 30 atm of H-2 or of ETSH from 4. The formation of the dihydride 2 from the vinylthiophenolate derivative 1 under H-2 (>15 atm) was also observed by HPNMR; this reaction was mimicked by the stepwise addition of H+ to yield [(triphos)Rh{eta(4)-S(C6H4)CH(CH3)}]BF4 (7) Reaction of the latter complex with H- produces (triphos)RhH[eta(2)-S(C6H4)CH(CH3)] (8), which converts to the dimer 3 by reductive coupling of the terminal hydride ligand with the metalated alkyl substituent in the thioligand, via the unsaturated fragment [(triphos)Rh{o-S(C6H4)C2H5}]. In the mechanistic picture proposed, the catalytically active species for both reactions is [(triphos)RhH] generated from 2 by the rate-determining reductive elimination of ETSH. The hydrogenation of BT to ETSH occurs after the substrate has been C-S inserted, although hydrogenation to DHBT also takes place as a minor, parallel path. Then eta(1)-S and eta(2)-2,3-BT isomers probably exist in equilibrium, but the eta(1)-S intermediate prevails over the eta(2)-2,3 isomer for steric reasons, thus determining the chemoselectivity of the reaction. The chemistry herein described provides further insight into the mechanistic aspects of HDS reactions on solid catalysts.

  DOI：

  10.1021/ja00138a011

文献信息

• Mimicking the HDS Activity of Promoted Tungsten Catalysts. A Homogeneous Modeling Study Using a Two-Component Tungsten/Rhodium System
  作者：Claudio Bianchini、M. Victoria Jiménez、Andrea Meli、Simonetta Moneti、Véronique Patinec、Francesco Vizza

  DOI：10.1021/om970711e

  日期：1997.12.1

  with CO (30 atm, 40 °C) gives the complex [(triphos)Rh(CO)2][(CO)5W(o-S(C6H4)C2H5)] (8), in which the thiolate ligand is η1-S bound to the tungsten atom in the complex anion [(CO)5W(o-S(C6H4)C2H5)]-. The hydrogenation of 8 (30 atm of H2, >70 °C) gives exclusively free 2-ethylthiophenol. The carbonylation of 2 (30 atm of CO, room temperature) results in the formation of [(triphos)Rh(CO)2][(CO)5W(o-S(C6H4)CHCH2)]

  W（CO）的反应5 THF与（三磷酸）的Rh [η 3 -S（C 6 H ^ 4）CH CH 2 ]（1），由16E的插入得到-片段[（三磷酸）RhH的]到C 2苯并[-S键b ]噻吩（BT），给出了二聚物（三磷酸）的Rh [η 3 - （CO）5 WS（C 6 H ^ 4）CH CH 2 ]（2 ;三膦=的MeC（CH 2 PPH 2）3）。与1不同，杂金属二聚体2与H反应2（30 atm）在THF中高于70°C，经历了由C-S插入的BT的脱硫。结果，获得了羰基氢化物（triphos）RhH（CO），乙苯和WS x（x av = 1.5）的混合物。在20至70°C的温度范围内进行高压NMR光谱分析表明，脱硫步骤先于二聚体（triphos）RhH（μ-H）[μ- o -S（C 6 H 4）C 2 H 5 ] W（CO）4（5），其中Rh和W中心通过桥接2-乙基硫代酚盐和氢化物配体而保持在一
• Like on Heterogeneous Hydrodesulfurization(HDS) Catalysts, the Homogeneous HDS of Benzo[b]thiophene Is Achived by the Concomitant Action of a Metal Promoter(Rh) and an Active HDS Component(W)
  作者：Claudio Bianchini、M. Victoria Jiménez、Carlo Mealli、Andrea Meli、Simonetta Moneti、Véronique Patinec、Francesco Vizza

  DOI：10.1002/anie.199617061

  日期：1996.8