(bis(1,3-bis(diphenylphosphino)ethane)(hydrido)ruthenium)PF6 | 154972-84-6

• 英文名称: (bis(1,3-bis(diphenylphosphino)ethane)(hydrido)ruthenium)PF6
• CAS: 154972-84-6
• 化学式: C₅₂H₄₉P₄Ru*F₆P
• 分子量: 1043.89
• InChiKey: FJSYGINXIUZTGS-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (bis(1,3-bis(diphenylphosphino)ethane)(hydrido)ruthenium)PF6 、 氘 以 四氢呋喃 为溶剂， 生成 (bis(1,4-bis(diphenylphosphino)ethane)(hydrido)ruthenium)PF6-d25
  参考文献：
  名称：

  配位不饱和钌配合物中的农业相互作用和分子内氢交换：螯合环大小对二膦配体的分子内碳氢键活化的影响

  摘要：

  The solution properties of formally five-coordinate ruthenium complexes [RuH(P-P)2]PF6 (P-P = 1,4-bis(diphenylphosphino)butane (dppb) (1a), 2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (diop) (1b), 1,3-bis(diphenylphosphino)propane (dppp) (1c), 1,2-bis(diphenylphosphino)ethane (dppe) (1d)) were examined by various NMR measurements. Variable temperature H-1 NMR measurements suggest that the behaviors of la and lb at low temperatures differ significantly from those at high temperature. The agostic interaction between an alpha-methylene CH moiety of the diphosphine ligand and the ruthenium center was detected in 1a below-30-degrees-C and in 1b below-60-degrees-C. In 1c and 1d no agostic interaction could be detected. The hydrogen exchanges among the terminal hydride, the agostic hydrogen, and a noncoordinating methylene hydrogen of dppb in la were proved on the basis of spin saturation transfer phenomena in the H-1 NMR measurements. The exchange rate between the agostic hydrogen and the terminal hydride was estimated in the temperature range -55 to -90-degrees-C by spin saturation transfer studies, to reveal that DELTAG(double dagger) for the hydrogen exchange is about 11 kcal mol-1. At high temperatures the hydrogen scrambling between ortho hydrogens on the phenyl groups, all the methylene hydrogens, and the terminal hydride in la was proved by employing the partially deuterized ligand Ph2P(CD2)4PPh2. Upon the contact of 1a, 1c, and 1d with D2 gas in solution, deuterium incorporation takes place at ortho and all methylene positions of diphosphines in these complexes. In the case of la, the deuterium content of each site is in the order beta-CH2 > alpha-CH2 > o-CH. In lb and 1c, the H/D exchange at o-CH proceeded in preference to those at alpha-CH2 or beta-CH2.

  DOI：

  10.1021/om00017a055