Rh^IIIHCl₂{^tBu₂P(CH₂)₅P^tBu₂} | 1443772-92-6

• 英文名称: Rh^IIIHCl₂{^tBu₂P(CH₂)₅P^tBu₂}
• 英文别名: [RhHCl₂{^tBu₂P(CH₂)₅P^tBu₂}]₂
• CAS: 1443772-92-6；72042-51-4；74806-51-2；74806-52-3
• 化学式: C₄₂H₉₄Cl₄P₄Rh₂
• 分子量: 1070.73
• InChiKey: GGEOVUZWRNSFSP-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  18.85
• 重原子数：
  52.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  碳酸甲丙酯 、 Rh^IIIHCl₂{^tBu₂P(CH₂)₅P^tBu₂} 反应 0.5h， 生成 HRhCl(HC(CH2P((t)Bu)2)2)
  参考文献：
  名称：

  Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O–O bond

  摘要：

  The reaction of RhCl3 center dot H2O with (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t afforded several complexes including [Rh-III(H)Cl{(Bu2P)-Bu-t(CH2)(2)CH(CH2)(2)(PBu2)-Bu-t}] (1). [(RhHCl2)-H-III{(Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t}](2) (2), [(RhCl)-Cl-I{(Bu2P)-Bu-t(CH2)(2)CH=(CHCH2PBu2)-Bu-t}] (3) and [(RhCl)-Cl-I{(Bu2PCH2C)-Bu-t(O)CH=(CHCH2PBu2)-Bu-t}] (4). X-ray crystal structures of 3 and 4 showed that the C=C bond on the C-5 unit of (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t is bound to Rh(I) in a eta(2) configuration. In 4, the Rh atom has a trigonal pyramidal coordination geometry. The X-ray crystal structure of 2 consists of two rhodium(III) centers bridged by two (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t ligands with two phosphorus atoms, one from each ligand, trans to one another. The crystal structure of the rhodium oxygen adduct with 1,3-bis(di-t-butyl-phosphinomethyl)benzene [RhO2{(Bu2PCH2)-Bu-t(C6H3)(CH2Bu2P)-Bu-t}] (5) was also investigated. In this species the O-2 is eta(2) coordinated to the Rh(l) center with asymmetric Rh-O bond lengths (2.087(7) and 1.998(8) angstrom). The O-O bond distance is short (1.337(11) angstrom) with v(o-o) of 990.5 cm(-1). DFT calculations on complex 5 yielded two eta(2)-O-2 structures that differed in energy by only 0.76 kcal/mol. The lower energy one (5a) had near C-2 symmetry, and had nearly equal Rh-O bond lengths, while the higher energy structure (5b) had near C-s symmetry and generally good agreement with the experimental structure. The calculated UV-Vis and IR spectra of complex 5 are in excellent agreement with experiment. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.10.006
• 作为产物：
  描述：

  rhodium(III) chloride trihydrate 、 1,5-二(二叔丁基膦)戊烷 以 水 、 异丙醇 为溶剂， 反应 65.0h， 以76%的产率得到Rh^IIIHCl₂{^tBu₂P(CH₂)₅P^tBu₂}
  参考文献：
  名称：

  Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O–O bond

  摘要：

  The reaction of RhCl3 center dot H2O with (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t afforded several complexes including [Rh-III(H)Cl{(Bu2P)-Bu-t(CH2)(2)CH(CH2)(2)(PBu2)-Bu-t}] (1). [(RhHCl2)-H-III{(Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t}](2) (2), [(RhCl)-Cl-I{(Bu2P)-Bu-t(CH2)(2)CH=(CHCH2PBu2)-Bu-t}] (3) and [(RhCl)-Cl-I{(Bu2PCH2C)-Bu-t(O)CH=(CHCH2PBu2)-Bu-t}] (4). X-ray crystal structures of 3 and 4 showed that the C=C bond on the C-5 unit of (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t is bound to Rh(I) in a eta(2) configuration. In 4, the Rh atom has a trigonal pyramidal coordination geometry. The X-ray crystal structure of 2 consists of two rhodium(III) centers bridged by two (Bu2P)-Bu-t(CH2)(5)(PBu2)-Bu-t ligands with two phosphorus atoms, one from each ligand, trans to one another. The crystal structure of the rhodium oxygen adduct with 1,3-bis(di-t-butyl-phosphinomethyl)benzene [RhO2{(Bu2PCH2)-Bu-t(C6H3)(CH2Bu2P)-Bu-t}] (5) was also investigated. In this species the O-2 is eta(2) coordinated to the Rh(l) center with asymmetric Rh-O bond lengths (2.087(7) and 1.998(8) angstrom). The O-O bond distance is short (1.337(11) angstrom) with v(o-o) of 990.5 cm(-1). DFT calculations on complex 5 yielded two eta(2)-O-2 structures that differed in energy by only 0.76 kcal/mol. The lower energy one (5a) had near C-2 symmetry, and had nearly equal Rh-O bond lengths, while the higher energy structure (5b) had near C-s symmetry and generally good agreement with the experimental structure. The calculated UV-Vis and IR spectra of complex 5 are in excellent agreement with experiment. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.10.006

文献信息

• Large-ring and cyclometalated rhodium complexes from some medium-chain .alpha.,.omega.-diphosphines
  作者：Christopher Crocker、R. John Errington、Richard Markham、Christopher J. Moulton、Kevin J. Odell、Bernard L. Shaw

  DOI：10.1021/ja00533a014

  日期：1980.6