[Rh(1,3-di(2-thionyl)-1,3-propanedionato)(CO)(PPh3)] | 1041404-34-5

• 英文名称: [Rh(1,3-di(2-thionyl)-1,3-propanedionato)(CO)(PPh3)]
• 英文别名: [Rh(dtm)(CO)(PPh3)]；[Rh(1,3-di(2-thenoyl)-1,3-propanedionate)(CO)(PPh3)]
• CAS: 1041404-34-5
• 化学式: C₃₀H₂₂O₃PRhS₂
• 分子量: 628.514
• InChiKey: RZVYERTTWFMFBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Rh(1,3-di(2-thionyl)-1,3-propanedionato)(CO)(PPh3)] 、 碘甲烷 以 氯仿 为溶剂， 生成 [Rh(Me)(I)(1,3-di(2-thionyl)-1,3-propanedionato)(CO)(PPh3)]
  参考文献：
  名称：

  Methyl iodide oxidative addition to monocarbonylphosphine [Rh((C4H3S)COCHCOR)(CO)(PPh3)] complexes utilizing UV/vis and IR spectrophotometry and NMR spectroscopy to identify reaction intermediates: R=C6H5 or C4H3S

  摘要：

  The chemical kinetics, studied by UV/vis and IR, of the oxidative addition of CH3I to [Rh((C4H3S) COCHCOR)(CO)(PPh3)], with R = C6H5 (Ph) or C4H3S, consists of three definite reaction steps and involves isomers of two distinctly different classes of a Rh-III-alkyl and two distinctly different classes of a Rh-III-acyl species according to the following reaction scheme:Rh-1+CH3 I[reversible arrow(K1,k1)(k-1){Rh-III-alkyl1]reversible arrow(K2,k2)(k-2)[Rh-III-acyl1]}reversible arrow(k3)(k-3)[R-III-alkyl2]reversible arrow(k4)(k-4) [Rh-III-acyl2]The molecular formulas of all the Rh-III-alkyl and Rh-III-acyl species are [Rh((C4H3S) COCHCOR)(CH3)(CO)(PPh3)(I)] and [Rh((C4H3S) COCHCOR)(COCH3)(PPh3)(I)] respectively, but the geometry is different due to different co-ordination positions of the ligands. The equilibrium K-2 was fast enough to be maintained during the Rh-I depletion in the first reaction step and during the Rh-III-alkyl2 formation in the second reaction step. A H-1 and P-31 NMR study of the oxidative addition of CH3I to the different isomers of [Rh((C4H3S) COCHCOC6H5)(CO)(PPh3)], containing an unsymmetrical beta-diketonato ligand, reveals the existence of at least two structural isomers for each reaction intermediate according to the following reaction scheme:[GRAPHICS]The observed rate of formation and depletion of the two Rh I isomers of the [Rh((C4H3S) COCHCO(C6H5))(CO)(PPh3)] complex, as well as the different isomers of each reaction intermediate, are the same, contrary to what was previously found for the formation of the alkyl2 isomers when R = CF3. All reaction intermediates are identified spectroscopically. (C) 2007 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.10.052
• 作为产物：
  描述：

  [Rh(1,3-di(2-thionyl)-1,3-propanedionato)(CO)2] 、 三苯基膦 以 氯仿 为溶剂， 以52.7%的产率得到[Rh(1,3-di(2-thionyl)-1,3-propanedionato)(CO)(PPh3)]
  参考文献：
  名称：

  Methyl iodide oxidative addition to monocarbonylphosphine [Rh((C4H3S)COCHCOR)(CO)(PPh3)] complexes utilizing UV/vis and IR spectrophotometry and NMR spectroscopy to identify reaction intermediates: R=C6H5 or C4H3S

  摘要：

  The chemical kinetics, studied by UV/vis and IR, of the oxidative addition of CH3I to [Rh((C4H3S) COCHCOR)(CO)(PPh3)], with R = C6H5 (Ph) or C4H3S, consists of three definite reaction steps and involves isomers of two distinctly different classes of a Rh-III-alkyl and two distinctly different classes of a Rh-III-acyl species according to the following reaction scheme:Rh-1+CH3 I[reversible arrow(K1,k1)(k-1){Rh-III-alkyl1]reversible arrow(K2,k2)(k-2)[Rh-III-acyl1]}reversible arrow(k3)(k-3)[R-III-alkyl2]reversible arrow(k4)(k-4) [Rh-III-acyl2]The molecular formulas of all the Rh-III-alkyl and Rh-III-acyl species are [Rh((C4H3S) COCHCOR)(CH3)(CO)(PPh3)(I)] and [Rh((C4H3S) COCHCOR)(COCH3)(PPh3)(I)] respectively, but the geometry is different due to different co-ordination positions of the ligands. The equilibrium K-2 was fast enough to be maintained during the Rh-I depletion in the first reaction step and during the Rh-III-alkyl2 formation in the second reaction step. A H-1 and P-31 NMR study of the oxidative addition of CH3I to the different isomers of [Rh((C4H3S) COCHCOC6H5)(CO)(PPh3)], containing an unsymmetrical beta-diketonato ligand, reveals the existence of at least two structural isomers for each reaction intermediate according to the following reaction scheme:[GRAPHICS]The observed rate of formation and depletion of the two Rh I isomers of the [Rh((C4H3S) COCHCO(C6H5))(CO)(PPh3)] complex, as well as the different isomers of each reaction intermediate, are the same, contrary to what was previously found for the formation of the alkyl2 isomers when R = CF3. All reaction intermediates are identified spectroscopically. (C) 2007 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.10.052

文献信息

• An experimental and DFT study of the packing and structure of dithenoylmethane monocarbonylphosphine Rhodium(I) complex [Rh((C 4 H 3 S)COCHCO(C 4 H 3 S))(CO)(PPh 3 )]
  作者：Marrigje Marianne Conradie、Petrus H.van Rooyen

  DOI：10.1016/j.jmgm.2018.04.016

  日期：2018.8

  NBO calculations revealed donor – acceptor NBO interactions between the lone pair on rhodium of one molecule and (i) the empty antibonding orbital on C-H of the nearest thienyl group of a neighbouring molecule, as well as with the (ii) the empty antibonding orbital on two carbons of the nearest thienyl group to rhodium on the neighbouring molecule.

  [Rh（（C 4 H 3 S）COCHCO（C 4 H 3 S））（CO）（PPh 3）]晶体在固态中以一维线性链堆叠，一个分子的噻吩基和相邻分子的β-二酮骨架的π堆叠略有滑动。由于两个芳族噻吩基和β-二酮基骨架的接近平面取向，观察到的堆积是可能的。实验观察到的堆积和紧密的分子间接触与理论QTAIM计算得出的相邻分子之间的分子间键合路径和分子间氢键相一致。NBO计算显示一个分子的铑上的孤对与（i）相邻分子的最接近噻吩基的CH上的空抗键轨道之间的供体-受体NBO相互作用，