RhICl{tBu2PCH2C(O)CH=CHCH2PtBu2} | 1443762-97-7

• 英文名称: RhICl{tBu2PCH2C(O)CH=CHCH2PtBu2}
• 英文别名: Rh^ICl{^tBu₂PCH₂C(O)CH=CHCH₂P^tBu₂}；RhCl{^tBu₂PCH₂COCH=CHCH₂P^tBu₂}
• CAS: 1443762-97-7
• 化学式: C₂₁H₄₀ClOP₂Rh
• 分子量: 508.854
• InChiKey: GBHCKXFYJGUKHQ-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：

  1,5-二溴戊烷 在 aluminum oxide 、 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 145.5h， 生成 RhICl{tBu2PCH2C(O)CH=CHCH2PtBu2}
  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