terakis(trimethylphosphite)hydridorhodium(I) | 59400-49-6

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: terakis(trimethylphosphite)hydridorhodium(I)
• CAS: 59400-49-6
• 化学式: C₁₂H₃₇O₁₂P₄Rh
• 分子量: 600.219
• InChiKey: GPNASEUMXLVBIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  29.0
• 可旋转键数：
  16.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  110.76
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为产物：
  描述：

  dimethylphosphonatotetrakis(trimethylphosphite)rhodium(I) 在 氢气 作用下， 以 not given 为溶剂， 生成 terakis(trimethylphosphite)hydridorhodium(I)
  参考文献：
  名称：

  由[M（P（OMe 3）5 ] 5 Cl]化合物（M = Rh，Ir）容易地形成铑和铱的膦酸酯络合物。二氢与[Mp（O）（OMe）2（P（OMe））之间的反应差异3）4 ]配合物（M = Co，Rh，Ir），包括铑磷键的易氢解

  摘要：

  从五元三亚磷酸三甲酯[M（P（OMe）3）3形成膦酸酯复合物[M（P（O）（OMe）2（P（OMe）3）4 ]（M = Rh，Ir））5 ] Cl，H 2与配合物[M'（P（O）（OMe）2（P（OMe）3）4），（M'= Co，Rh，Ir）的相互作用差异为介绍和讨论。

  DOI：

  10.1016/0022-328x(86)80155-3

文献信息

• Synthesis and reactivity of trimethylphosphite complexes of cobalt, rhodium and iridium. Crystal and molecular structure of [IrH(P(OMe)3)4(P(OMe)2OSnMe2Cl2)][SnCl3Me2]
  作者：Peter B. Hitchcock、Stanlei I. Klein、John F. Nixon

  DOI：10.1016/0022-328x(83)80035-7

  日期：1983.1

  Syntheses of [M(P(O)(OMe)2)(P(OMe)3)4] (M = Co, Rh, Ir) are reported and variable temperature 31P NMR studies on the iridium complex are described. Hydrogen reacts differently with the Ir and Rh complexes giving (IrH2(P(O)(OMe)2)(P(OMe)3)3] and [RhH(P(OMe3)4], respectively. The crystal and molecular structure of the novel compound [IrH(P(OMe)3)4(P(OMe)2OSnMe2Cl2)][SnCl3Me2] is described.

  报告了[M（P（O）（OMe）2）（P（OMe）3）4 ]（M = Co，Rh，Ir）的合成，并描述了铱配合物的可变温度31 P NMR研究。氢与Ir和Rh的络合物反应不同，分别得到（IrH 2（P （Oe （OMe）2）（P（OMe）3）3）3 ]和[RhH（P（OMe 3）4）。描述了新型化合物[IrH（P（OMe）3）4（P（OMe）2 OSnMe 2 Cl 2）] [SnCl 3 Me 2 ]的结构。
• Mono- and bis[bis(diphenylphosphino)methane]-bridged Ru-Rh complexes. Preparation, Characterization, and reactivity. X-ray crystal structure of RuRhH(Ph)(PhPCH2PPh2)(Ph2PCH2PPh2)(C8H12).cntdot.1/2PhMe and of RuHCl(Ph2PCH2PPh2)2.cntdot.1/2PhMe
  作者：Beatrice. Delavaux、Bruno. Chaudret、Jean. Devillers、Francoise. Dahan、Gerard. Commenges、Rene. Poilblanc

  DOI：10.1021/ja00273a026

  日期：1986.6

  The reaction of RuCOD(dppm)/sub 2/ (COD = cis,cis-1,5-cyclooctadiene, dppm = bis(diphenylphosphino)methane) with (RhCl(CO)/sub 2/)/sub 2/ affords Ru(CO)(COD)(dppm) and (RhCl(CO)dppm)/sub 2/ at room temperature after ligand exchange. At 80/sup 0/C two further products are obtained, Rh/sub 2/Cl/sub 2/CO(dppm)/sub 2/ and RuRhCl(CO)/sub 3/(dppm)/sub 2/. A mechanism is proposed. Full spectroscopic characterization

  RuCOD(dppm)/sub 2/ (COD = cis,cis-1,5-环辛二烯, dppm = 双(二苯基膦)甲烷) 与 (RhCl(CO)/sub 2/)/sub 2/ 反应得到 Ru( CO)(COD)(dppm) 和 (RhCl(CO)dppm)/sub 2/ 在室温下配体交换后。在 80/sup 0/C 下获得另外两种产物，Rh/sub 2/Cl/sub 2/CO(dppm)/sub 2/ 和 RuRhCl(CO)/sub 3/(dppm)/sub 2/。提出了一种机制。描述了新配合物的完整光谱表征，即 /sup 1/H、/sup 13/C 和 /sup 31/P NMR 以及 /sup 103/Rh 共振频率的测定。描述了 RuHCl(dppm)/sub 2/ x 1/2PhMe 和 RuRhH(Ph)(ThPCH/sub 2/PPh/sub 2/)(dppm)(COD) 的晶体结构。
• Rhodium pentafluorophenylthiolate complexes derived from [Rh2(μ-SC6F5)2(PPh3)4]
  作者：Laurence Carlton

  DOI：10.1016/0022-328x(92)83289-t

  日期：1992.6

  [Rh(SC6F5)(PR3)3] and [cis-Rh(SC6F5)(PPh3)2(L)] combine reversibly, [cis-Rh(SC6F5)(PPh3)2(L′)] does not react and [Rh(SC6 F5)P(OR′)3}3] (in the presence of free P(OR′)3) is converted into [RhHP(OR′)3}4]. [Rh(SC6F5)(PR 3)3] and [cis-Rh(SC6F5)(PPh3)2(L)] react with phenylacetylene to give [RhH(SC6F5)(C2Ph)(PR3)3] and [RhH(SC6F5)(C2Ph)(PPh3)2(L)], respectively, while with C6F5SH [cis-Rh(SC6F5)(PPh3)2(L)] forms

  的的[Rh硫醇盐桥2（μ-SC 6 ˚F 5）2（PPH 3）4 ]可容易地通过各种膦，亚磷酸酯和含氮化合物的拆分，得到的[Rh（SC 6 ˚F 5）（PR 3）3 ]，[Rh（SC 6 F 5）P（OR'）3 } 3 ]，[顺式-Rh（SC 6 F 5）（PPh 3）2（L）]和[顺式-Rh（SC 6） F 5）（PPh 3）2（L'）]，（PR 3 = PMe 2 Ph，PMePh 2 ; P（OR'）3 = P（OMe）3，P（OEt）3 ; L（在空间上不受阻碍）=吡啶，3-甲基吡啶，异喹啉，N-甲基咪唑，乙腈； L'（位阻）＝ 2-甲基吡啶，2，6-二甲基吡啶，喹啉）。在环境条件下使用H 2时，[Rh（SC 6 F 5）（PR 3）3 ]和[顺式-Rh（SC 6 F 5）（PPh 3）2（L）]都可逆地结合，[顺式-Rh（SC）6 F 5）（PPh 3）2（L'）]不反应，[Rh（SC
• Toluene-solvated rhodium atoms: Evidence for a hydridorhodium complex
  作者：Giovanni Vitulli、Gloria Uccello-Barretta、Paolo Pannocchia、Andrea Raffaelli

  DOI：10.1016/0022-328x(86)80074-2

  日期：1986.3
• Hydroformylation of oct-1-ene catalyzed by dinuclear gem-dithiolato-bridged rhodium(I) complexes and phosphorus donor ligands
  作者：Angel B. Rivas、Jesús J. Pérez-Torrente、Alvaro J. Pardey、Anna M. Masdeu-Bultó、Montserrat Diéguez、Luis A. Oro

  DOI：10.1016/j.molcata.2008.10.046

  日期：2009.3

  The dinuclear gem-dithiolato bridged compounds [Rh-2(mu-S(2)Cptn)(cod)(2)] (1) (CptnS(2)(2-) = 1,1-cyclopentanedithiolato), [Rh-2(mu-S(2)Chxn)(cod)(2)] (2) (ChxnS(2)(2-) = 1,1-cyclohexanedithiolato), [Rh-2(mu-S2CBn2)(cod)(2)] (3) (Bn2CS22- = 1,3-diphenyl-2,2-dithiolatopropane) and [Rh-2(mu-(S2CPr2)-Pr-i)(cod)(2)] (4) ((Pr2CS22-)-Pr-i = 2,4-dimethyl-2,2-dithiolatopentane) dissolved in toluene in the presence of monodentate phosphine or phosphite P-donor ligands under carbon monoxide/hydrogen (1: 1) atmosphere are efficient catalysts for the hydroformylation of oct-1-ene under mild conditions (6.8 atm of CO/H-2 and 80 degrees C). The influence of the gem-dithiolato ligand, the P-donor co-catalyst and the P/Rh ratio on the catalytic activity and selectivity has been explored. Aldehyde selectivities higher than 95% and turnover frequencies Lip to 245 h(-1) have been obtained using P(OMe)(3) as modifying ligand. Similar activity figures have been obtained using P(OPh)(3) although the selectivities are lower. Regioselectivities toward linear aldehyde are in the range 75-85%. The performance of the catalytic systems [Rh-2(mu-S2CR2)(CO)(2)(PPh3)(2)]/PPh3 has been found to be comparable to the systems [Rh-2(mu-S2CR2)(cod)(2)] at the same P/Rh ratio. The system [Rh-2(mu-S2CBn2)(cod)(2)] (3)/P(OPh)(3) has been tested in the hydroformylation-isomerization of trans-oct-2-ene. Under optimized conditions tip to 54% nonanal was obtained. Spectroscopic studies under pressure (HPNMR and HPIR) evidenced the formation of hydrido mononuclear species under catalytic conditions that are most probably responsible for the observed catalytic activity. (C) 2008 Elsevier B.V. All rights reserved.