| 166330-14-9

• CAS: 166330-14-9
• 化学式: C₅₈H₄₈O₂P₃Rh
• 分子量: 973.834
• InChiKey: UONGHWVQWOQEOB-APZHMLOSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  4,5-双二苯基膦-9,9-二甲基氧杂蒽 、 C13取代的一氧化碳 、 三(三苯基膦)羰基氢化铑 以 苯 为溶剂， 生成
  参考文献：
  名称：

  New Diphosphine Ligands Based on Heterocyclic Aromatics Inducing Very High Regioselectivity in Rhodium-Catalyzed Hydroformylation: Effect of the Bite Angle

  摘要：

  The effect of the bite angle on regioselectivity in the rhodium-catalyzed hydroformylation reaction was studied with a series of bidentate diphosphines based on xanthene-like backbones as ligands. The bite angles of these ligands are fine-tuned by subtle alterations of the backbone of the ligands. When the bridge (X) in the 10-position of xanthene is varied, the bite angle as calculated from molecular mechanics increases stepwise from 102 to 131 degrees, whereas the changes in steric bulk and electronic effects are virtually absent for the following ligands: bis(2-(diphenylphosphino)phenyl) ether (DPEphos, 1), X = H, H; 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos, 2), X = Si(CH3)(2); 2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin (Thixantphos, 3), X = S; 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene (Xantphos, 4), X = C(CH3)(2); 4,6-bis(diphenylphosphino)dibenzofuran (DBFphos, 5), X = bond. In the hydroformylation of 1-octene the regioselectivity increased. regularly with increasing bite angle: at 40 degrees C up to 98.3% n-aldehyde was obtained with Xantphos, without isomerization or hydrogenation of 1-octene. DBFphos does not form chelates, and consequently no increased selectivity was observed. The selectivity of the catalyst was almost unaffected by raising of the temperature to 80 degrees C, resulting in a higher turnover frequency (tof) with a constant selectivity: 97.7% n-aldehyde, 0.5% isomerization, and a tof value of 800 mol (mel of Rh)(-1) h(-1). Xantphos induces the highest selectivity for the formation of the linear aldehyde reported for diphosphines in the hydroformylation of 1-alkenes until now. The complexes (diphosphine)Rh(H)(CO)(PPh(3)) and (diphosphine)Rh(H)(CO)(2) were prepared and identified with H-1, P-31, and C-13 NMR. The enhanced selectivity to the linear aldehyde was also observed for styrene (70% n-aldehyde with xantphos compared to 11% with triphenylphosphine). An X-ray crystal structure of the Xantphos ligand is presented (orthorhombic, space group Pbnm, with a = 8.7678(8) Angstrom, b = 18.967(1) Angstrom, c = 19.181(1) Angstrom, V = 3189.8(4) Angstrom(3), and Z = 4).

  DOI：

  10.1021/om00006a057