{Rh2(CO)2(μ-DMAD)(dmpm)2} | 141613-94-7

• 英文名称: {Rh2(CO)2(μ-DMAD)(dmpm)2}
• CAS: 141613-94-7
• 化学式: C₁₈H₃₄O₆P₄Rh₂
• 分子量: 676.17
• InChiKey: NJSATWMCNOANEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为反应物：
  描述：

  {Rh2(CO)2(μ-DMAD)(dmpm)2} 、 六氟-2-丁炔 生成 {Rh2(CO)2(μ-DMAD)(μ-HFB)(dmpm)2}
  参考文献：
  名称：

  Novel binuclear bis(dimethylphosphino)methane-bridged complexes of rhodium containing two and three alkyne molecules

  摘要：

  The bis(alkyne) complexes [Rh2(CO)2(mu-RC=CR)(mu-R'C=CR')(dmpm)2] (R = R'= CO2Me (1); R = CO2Me, R' = CF3 9.833 dmpm = Me2PCH2PMe2) are prepared by addition of dimethyl acetylenedicarboxylate to [Rh2(CO)2(mu-RC=CR) (dmpm)2] (R = CO2Me, CF3). Addition of excess hexafluorobutyne (HFB) to [Rh2(CO)2(mu-HFB)(dmpm)2] yields [Rh2(HFB)2(mu-CO)(mu-HFB)(dmpm)2] (4), in which one alkyne is eta-2-bound to each rhodium while the third is bridging. Reaction of 4 with carbon monoxide yields [Rh2(CO)2(eta-2-HFB)(mu-HFB)(dmpm)2] (5), containing one terminal and one bridging HFB group, and this species rearranges to [Rh2(CO)2(mu-HFB)2(dmpm)2] (3), analogous to species 1 and 2. All bis(alkyne) complexes 1-3 are unreactive and do not react with CO OT With additional alkyne. The structures of 2 and 3 have been determined. Compound 2 crystallizes in the triclinic space group P1BAR with a = 9.7825 (8) angstrom, b = 9.833 (1) angstrom, c = 9.3791 (9) angstrom, alpha = 92.390 (8)-degrees, beta = 99.893 (7)-degrees, gamma = 118.180 (8)-degrees, V = 775.5 angstrom3, and Z = 1, while 3 crystallizes in the monoclinic space group P2(1)/n with a = 9.474 (1) angstrom, b = 15.813 (2) angstrom, c = 9.917 (1) angstrom, beta = 95.34 (1)-degrees, V = 1479.3 angstrom3, and Z = 2. For compound 2 the disorder present affects only the substituents on the alkynes (CO2Me, CF3); all other atoms are well behaved. In spite of this disorder in 2 all atoms refined well, converging to R = 0.030 and R(w) = 0.049 based on 2486 observations. Compound 3 refined to R = 0.040 and R(w) = 0.043 based on 1588 observations. Both compounds have a trans arrangement of diphosphines with the alkynes bound on opposite faces of the complex as cis-dimetalated olefins. The Rh-Rh separations of 2.6989 (4) angstrom (2) and 2.696 (1) angstrom (3) are quite short; however, all parameters associated with the alkyne ligands are as expected for this binding mode.

  DOI：

  10.1021/om00044a015
• 作为产物：
  描述：

  {Rh2Cl2(CO)2(μ-DMA)(DMPM)2} 、 sodium tetrahydroborate 以 乙醇 、 水 为溶剂， 以60-70的产率得到{Rh2(CO)2(μ-DMAD)(dmpm)2}
  参考文献：
  名称：

  Unusual low-valent dirhodium complexes bridged by bis(dimethylphosphino)methane ligands

  摘要：

  The low-valent complex [Rh2(CO)3(dmpm)2] (1) (dmpm = Me2PCH2PMe2) is prepared by the reaction of trans-[RhCl(CO)(dmpm)]2 with aqueous NaOH and CO. Under a CO atmosphere 1 is in equilibrium with the labile tetracarbonyl species [Rh(CO)(mu-CO)(dmpm)]2 (2). The structure of 1 is believed to be unsymmetrical having a trans arrangement of diphosphine ligands at one metal and a cis arrangement at the other, and a mixed-valence Rh(1+)/Rh(1-) formulation, while 2 is symmetric having the bridging diphosphines cis at both metals, and a corresponding Rh(0)/Rh(0) formulation. Reduction of [Rh2Cl2-(CO)2(mu-RC=CR)(dmpm)2] (R = CO2Me, CF3) yields [Rh2(CO))2(mu-RC=CR)(dmpm)2] (3, 4), which can also be obtained by alkyne addition to 1. The alkyne ligands are apparently bound perpendicular to the Rh-Rh axes in both species. Protonation of 1 with HBF4.OEt2 yields [Rh2(CO)3(mu-H)(dmpm)2][BF4], and under carbon monoxide this yields [Rh2(CO)4(mu-H)(dmpm)2][BF4]. Protonation of 3 yields [Rh2(CO)2-(mu-DMAD)(mu-H)(dmpm)2][BF4], whereas protonation of 4 yields [Rh2(CO)2(CF3C=C(H)CF3)(dmpm)2] [BF4], which apparently has a sigma, pi-vinylic moiety. Reaction of this vinyl complex with CO gives [Rh2(CO)3-(CF3C=C(H)CF3)(mu-CO)(dmpm)2][BF4] in which the vinyl group is sigma-bound to only one metal.

  DOI：

  10.1021/om00044a014