H4Ru4(CO)84 | 185411-21-6

• 英文名称: H4Ru4(CO)84
• CAS: 185411-21-6
• 化学式: C₅₆H₈₈O₃₂P₄Ru₄
• 分子量: 1801.47
• InChiKey: MSOPTGPKBHZVQA-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  H4(ruthenium)4(carbonyl)12 、 Bis(propanoyloxymethyl)phosphanylmethyl propanoate 以 正庚烷 为溶剂， 以74%的产率得到H4Ru4(CO)84
  参考文献：
  名称：

  氢存在下被功能化膦取代的氢化钌羰基簇的合成，表征和行为。1. H 4 Ru 4（CO）8 [P（CH 2 OCOR）3 ] 4（R = CH 3-，C 2 H 5 -，（CH 3）2 CH-，（CH 3）3 C-，（S）-C 2 H 5 CH（CH 3）-）

  摘要：

  含酯基P（CH 2 OCOR）3（R = CH 3-，C 2 H 5 -，（CH 3）2 CH-，（CH 3）3 C-，（S）-C的膦的合成与表征报告了2 H 5 CH（CH 3）-）。新的氢化钌络合物H 4 Ru 4（CO）8 [P（CH 2 OCOR）3 ] 4（R = CH 3-，C 2 H 5 -，（CH 3）合成并表征了2 CH-，（CH 3）3 C-，（S）-C 2 H 5 CH（CH 3）-）。通过X射线衍射确定（+）-（S）-H 4 Ru 4（CO）8 {P [CH 2 OCOCH（CH 3）C 2 H 5 ] 3 } 4的结构。已经研究了这些络合物在25-130°C温度范围内的压力（130个大气压）下于氢的烃溶液中的行为。配体P（CH 2 OCOR）3中存在的酯基将其在温和条件下氢化，形成相应的醇RCH 2 OH。

  DOI：

  10.1021/om960037l
• 作为试剂：
  描述：

  丙酸 在 H4Ru4(CO)84 氢气 作用下， 以 neat (no solvent) 为溶剂， 反应 48.0h， 生成 丙醇 、 丙酸正丙酯
  参考文献：
  名称：

  The role of functionalized phosphines in the hydrogenation of carboxylic acids in the presence of phosphine substituted hydrido ruthenium complexes

  摘要：

  Hydride ruthenium carbonyl complexes substituted by functionalized phosphines such as H4Ru4(CO)(8)[P(CH2OCOR)(3)](4) have been synthesized and tested as catalysts in the hydrogenation of carboxylic acids. These complexes are more active than those reported previously, containing trialkyl- or triarylphosphines. On the basis of their behavior, their different activity has been explained in terms of an involvement of the phosphine ligand in the catalytic cycle. The ester group present in the phosphine P(CH2OCOR)(3) is hydrogenated to produce an alcohol (RCH2OH) and a P(CH2OH) group which, in turn, reacts with the free acid present in solution to restore the P(CH2OCOR) group. This hypothesis has been confirmed by the reactivity of the possible intermediate H4Ru4(CO)(8)[P(CH2OH)(3)](4) with acetic acid. Another support to this statement is the almost equal catalytic activity, displayed by H4Ru4(CO)(8)[P(CH2OCOR)(3)](4) complexes, whatever the R group present, in the phosphine ligand, in the hydrogenation of carboxylic acids. These complexes, on the other hand, are less active than the corresponding tributylphosphine substituted ones in the hydrogenation of alkenes and ketones. Finally when the phosphine ligand is P(CH2CH2COOCH3)(3) the ester group is not reduced and consequently the catalytic activity of this complex in the hydrogenation of carboxylic acids is very low. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00038-8