thixantphos-Me | 214050-05-2

• 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: thixantphos-Me
• 英文别名: (2,8-Dimethylphenoxathiine-4,6-diyl)bis(di-p-tolylphosphine)；[6-bis(4-methylphenyl)phosphanyl-2,8-dimethylphenoxathiin-4-yl]-bis(4-methylphenyl)phosphane
• CAS: 214050-05-2
• 化学式: C₄₂H₃₈OP₂S
• 分子量: 652.777
• InChiKey: UYKLVFPHRZVLMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.2
• 重原子数：
  46
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1,5-cyclooctadiene)(1,3,5-cyclooctatriene)ruthenium 、 氢气 、 thixantphos-Me 以 四氢呋喃 为溶剂， 以72%的产率得到cis-RuH2(thixantphos-CH3)2
  参考文献：
  名称：

  Ruthenium Dihydrogen Complexes with Wide Bite Angle Diphosphines

  摘要：

  The wide bite angle diphosphines homoxantphos (10,11-dihydro-4,5,-bis(diphenylphosphino)dibenzo[b,f]oxepine), sixantphos (4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin), and thixantphos (2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin) were used to prepare cis[MH2(diphosphine)(2)] complexes (1a-f) by reaction of [Ru(cod)(cot)] (cod = cyclo-octa-1,5-diene, cot = cyclo-octa-1,3,5-triene) with 2 equiv of the diphosphine under dihydrogen pressure. The electronic properties of the thixantphos ligand were varied. Complexes 1a-f can be protonated with HBF4 or CF3COOH to yield hydrido(dihydrogen) complexes cis[MH(H-2)(diphosphine)(2)](+) (2a-f), which were characterized by VT (variable temperature) NMR and T-1 measurements. These complexes show fast hydrogen atom exchange between the eta(2)-H-2 and the terminal hydride at all temperatures studied. They are thermally unstable toward dihydrogen loss yielding the cationic monohydride complexes cis[MH(diphosphine)(2)](+) (3a-f). Coordination of the eta(2)-H-2 is dominated by sigma --> d donation, and hence, the H-H distance is hardly influenced by the electronic properties of the ligands.

  DOI：

  10.1021/ic020577c
• 作为产物：
  描述：

  对甲苯基溴化镁 、 4,5-bis(dichlorophosphino)-2,7-dimethylphenoxathiin 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 thixantphos-Me
  参考文献：
  名称：

  二膦铑催化氢甲酰化的电子效应：重新考虑咬角效应

  摘要：

  研究了铑二膦催化的加氢甲酰化中的电子效应。合成了一系列电子修饰的thixantphos配体，并研究了它们对配位化学和催化性能的影响。通过在二苯基膦部分上使用 p-(CH3)2N、p-CH3O、pH、pF、p-Cl 或 p-CF3 取代基来改变膦的碱度。获得配合物(thixantphos)Rh(CO)H(PPh3)和(p-CH3O-thixantphos)Rh(CO)H(PPh3)的X射线晶体结构测定。(二膦)Rh(CO)H(PPh3)和(二膦)Rh(CO)2H配合物的溶液结构通过红外光谱和核磁共振光谱进行了研究。IR 和 1H NMR 光谱表明 (diphosphine)Rh(CO)2H 配合物由双赤道 (ee) 和赤道顶 (ea) 异构体的动态平衡组成。证明平衡组成取决于膦碱度；ee:ea 异构体比例逐渐从 p-(CH3)2N-取代配体的几乎 1 变为 p-CF3-subs 的超过 9.

  DOI：

  10.1021/ja981969e

文献信息

• Electronic Effect on Rhodium Diphosphine Catalyzed Hydroformylation: The Bite Angle Effect Reconsidered
  作者：Lars A. van der Veen、Maarten D. K. Boele、Frank R. Bregman、Paul C. J. Kamer、Piet W. N. M. van Leeuwen、Kees Goubitz、Jan Fraanje、Henk Schenk、Carles Bo

  DOI：10.1021/ja981969e

  日期：1998.11.1

  The electronic effect in the rhodium diphosphine catalyzed hydroformylation was investigated. A series of electronically modified thixantphos ligands was synthesized, and their effects on coordination chemistry and catalytic performance were studied. Phosphine basicity was varied by using p-(CH3)2N, p-CH3O, p-H, p-F, p-Cl, or p-CF3 substituents on the diphenylphosphine moieties. X-ray crystal structure

  研究了铑二膦催化的加氢甲酰化中的电子效应。合成了一系列电子修饰的thixantphos配体，并研究了它们对配位化学和催化性能的影响。通过在二苯基膦部分上使用 p-(CH3)2N、p-CH3O、pH、pF、p-Cl 或 p-CF3 取代基来改变膦的碱度。获得配合物(thixantphos)Rh(CO)H(PPh3)和(p-CH3O-thixantphos)Rh(CO)H(PPh3)的X射线晶体结构测定。(二膦)Rh(CO)H(PPh3)和(二膦)Rh(CO)2H配合物的溶液结构通过红外光谱和核磁共振光谱进行了研究。IR 和 1H NMR 光谱表明 (diphosphine)Rh(CO)2H 配合物由双赤道 (ee) 和赤道顶 (ea) 异构体的动态平衡组成。证明平衡组成取决于膦碱度；ee:ea 异构体比例逐渐从 p-(CH3)2N-取代配体的几乎 1 变为 p-CF3-subs 的超过 9.
• Ruthenium Dihydrogen Complexes with Wide Bite Angle Diphosphines
  作者：Karina Almeida Leñero、Mirko Kranenburg、Yannick Guari、Paul C. J. Kamer、Piet W. N. M. van Leeuwen、Sylviane Sabo-Etienne、Bruno Chaudret

  DOI：10.1021/ic020577c

  日期：2003.5.1

  The wide bite angle diphosphines homoxantphos (10,11-dihydro-4,5,-bis(diphenylphosphino)dibenzo[b,f]oxepine), sixantphos (4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin), and thixantphos (2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin) were used to prepare cis[MH2(diphosphine)(2)] complexes (1a-f) by reaction of [Ru(cod)(cot)] (cod = cyclo-octa-1,5-diene, cot = cyclo-octa-1,3,5-triene) with 2 equiv of the diphosphine under dihydrogen pressure. The electronic properties of the thixantphos ligand were varied. Complexes 1a-f can be protonated with HBF4 or CF3COOH to yield hydrido(dihydrogen) complexes cis[MH(H-2)(diphosphine)(2)](+) (2a-f), which were characterized by VT (variable temperature) NMR and T-1 measurements. These complexes show fast hydrogen atom exchange between the eta(2)-H-2 and the terminal hydride at all temperatures studied. They are thermally unstable toward dihydrogen loss yielding the cationic monohydride complexes cis[MH(diphosphine)(2)](+) (3a-f). Coordination of the eta(2)-H-2 is dominated by sigma --> d donation, and hence, the H-H distance is hardly influenced by the electronic properties of the ligands.