hydrido(π-phenoxo)bis(triphenylphosphine)ruthenium(II) | 61817-37-6

• 英文名称: hydrido(π-phenoxo)bis(triphenylphosphine)ruthenium(II)
• 英文别名: [ruthenium(hydride)(η⁵-C6H5O)(PPh3)2]；RuH(η5-phenoxide)(PPh3)2
• CAS: 61817-37-6
• 化学式: C₄₂H₃₆OP₂Ru
• 分子量: 719.765
• InChiKey: ZHVVOEKRALUJKR-UHFFFAOYSA-N

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

• 作为反应物：
  描述：

  hydrido(π-phenoxo)bis(triphenylphosphine)ruthenium(II) 、 氘代氯仿 以 氘代氯仿 为溶剂， 生成 RuCl(η5-phenoxide)(PPh3)2
  参考文献：
  名称：

  The kinetic instability of σ-bound aryloxide in coordinatively unsaturated or labile complexes of ruthenium

  摘要：

  Reaction of RuCl2(PPh3)(3) (1) or RuHCl(PPh3)(3) (2) with KOAr (Ar = 4-(BuC6H4)-Bu-t) in non-alcohol solvents affords pi-aryloxide derivatives Ru(eta(5)-ArO)(o-C6H4PPh2)(PPh3) (3a) or RuH(eta(5)-ArO)(PPh3)(2) (6a), respectively. The phenoxide analogues 3b and 6b are obtained on use of KOPh or TIOPh. Treatment of 1 with 1 equiv. KOAr in the presence of isopropanol liberates the phenol and acetone, affording clean 2 in quantitative yields. In 3:1 methanol-CH2Cl2, RuHCl(CO)(PPh3)(3) (4) is also formed in small amounts. eaction of 1 with 2 KOAr in 20% MeOH-CH2Cl2 affords a mixture of 6a and RuH2(CO)(PPh3)(3) (5). In the corresponding reaction of 2 with 1 KOAr, sigma-pi isomerization of the sigma-aryloxide ligand dominates, affording 6a(.)MeOH as the principal product. Treatment of 6a with ethereal HCl gives [RuH(eta(6)-ArOH)(PPh3)(2)]Cl (7a); the corresponding reaction of 6b yields Rucl(eta(5)- PhO)(PPh3)(2) (8b). The crystal structures of 3a, 3b, 4, 5, 7a, and 8b are reported. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01347-6
• 作为产物：
  描述：

  hydridochlorotris(triphenylphosphine)ruthenium(II) 、 thallous phenoxide 以 四氢呋喃 为溶剂， 生成 hydrido(π-phenoxo)bis(triphenylphosphine)ruthenium(II)
  参考文献：
  名称：

  The kinetic instability of σ-bound aryloxide in coordinatively unsaturated or labile complexes of ruthenium

  摘要：

  Reaction of RuCl2(PPh3)(3) (1) or RuHCl(PPh3)(3) (2) with KOAr (Ar = 4-(BuC6H4)-Bu-t) in non-alcohol solvents affords pi-aryloxide derivatives Ru(eta(5)-ArO)(o-C6H4PPh2)(PPh3) (3a) or RuH(eta(5)-ArO)(PPh3)(2) (6a), respectively. The phenoxide analogues 3b and 6b are obtained on use of KOPh or TIOPh. Treatment of 1 with 1 equiv. KOAr in the presence of isopropanol liberates the phenol and acetone, affording clean 2 in quantitative yields. In 3:1 methanol-CH2Cl2, RuHCl(CO)(PPh3)(3) (4) is also formed in small amounts. eaction of 1 with 2 KOAr in 20% MeOH-CH2Cl2 affords a mixture of 6a and RuH2(CO)(PPh3)(3) (5). In the corresponding reaction of 2 with 1 KOAr, sigma-pi isomerization of the sigma-aryloxide ligand dominates, affording 6a(.)MeOH as the principal product. Treatment of 6a with ethereal HCl gives [RuH(eta(6)-ArOH)(PPh3)(2)]Cl (7a); the corresponding reaction of 6b yields Rucl(eta(5)- PhO)(PPh3)(2) (8b). The crystal structures of 3a, 3b, 4, 5, 7a, and 8b are reported. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01347-6

文献信息

• Exploring the Variable Hapticity of the Arylamide Ligand: Access to σ-Amidophenyl and π-Cyclohexadienylimine Structures
  作者：Benjamin J. Ireland、Robert McDonald、Deryn E. Fogg

  DOI：10.1021/om4005252

  日期：2013.9.9

  A study of the preference for sigma vs pi coordination of the arylamido ligand to a late transition metal shows that LiNPh2 reacts with RuHCl(PPh3)(3) (1) to yield the bent-seat piano-stool complex RuH[(eta(5)-C6H5)NPh](PPh3)(2) (2a) but with RuHCl(CO)(PPh3)(3) (3) to yield the sigma-amide RuH(eta(1)-NPh2)(CO)(PPh3)(2) (4). The stability of the sigma-bound NPh2 ligand in 4 reflects the pi acidity of the CO ligand, which inhibits PPh3 loss. Carbonylation of 2a at 50 degrees C affords Ru(CO)(3)(PPh3)(2) (8) and HNPh2, suggesting sequential pi -> sigma a isomerization and reductive elimination. The phenoxide ligand behaves similarly: RuH(eta(5)-C6H5O)(PPh3)(2) (2b) is formed from 1 but RuH(eta(1)-OPh)(CO)(PPh3)(3) (5) is formed from 3, and carbonylation of 2b gives 8 and phenol, although more forcing conditions are required (90 degrees C). The crystal structure of 2a is reported.