fac,cis-[RhCl3(CO)(PMe3)2] | 862297-85-6

• 英文名称: fac,cis-[RhCl3(CO)(PMe3)2]
• CAS: 862297-85-6
• 化学式: C₇H₁₈Cl₃OP₂Rh
• 分子量: 389.431
• InChiKey: PPQSJINSLBBMLS-UHFFFAOYSA-K

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：
  None
• 环数：
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• 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

• 作为产物：
  描述：

  氯羰基双(三甲基膦)铑(I) 在 Cl₂ 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到fac,cis-[RhCl3(CO)(PMe3)2]
  参考文献：
  名称：

  金，钯，铂，铑和铱的某些羰基配合物的振动和核磁共振光谱研究

  摘要：

  报告了有关[AuCl（CO）]，[PtX 3（CO）] –（X = Cl，Br或I），[PdX 3（CO）] –，顺式[PtX 2（CO ）2 ]，顺式-[RhX 2（CO）2 ] –（X = Cl或Br）和顺式-[IrCl 2（CO）2 ] –以及赋值。骨骼拉伸波数报道了顺式- [PTX 2（CO）（PME 3）]（X =氯，溴，或I），反式- [PTX（CO）（PME 3）2] +，反式-[RhX（CO）（PMe 3）2 ]（X = Cl或Br）和[RhCl 3（CO）（PMe 3）2 ]。报道了13 C nmr对碳配合物的研究结果，以及1 H nmr和1 H- { 31 p}和1 H- { 195 Pt} INDOR光谱对含膦配合物的研究结果。[PtX 3（CO）]的195 Pt化学位移–来自直接测量的报告。在一些较简单的配合物的拉伸力常数的帮助下讨论了结果。

  DOI：

  10.1039/dt9770002061

文献信息

• Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex
  作者：Taigo Kashiwabara、Masato Tanaka

  DOI：10.1021/om101079e

  日期：2011.1.24

  Reactions of ArCOCOCl (Ar = p-ClC(6)H(4), Ph) with Rh(acac)(CO)(2) proceeded readily to afford dimeric arylglyoxyl rhodium complexes [Rh(mu-Cl)(acac)(CO)(COCOAr)](2). [Rh(mu-Cl)(acac)(CO)COCO(p-ClC(6)H(4))}](2) was characterized by X-ray diffraction. Thermolysis of the products showed that [Rh(mu-Cl)(acac)(CO)COCO(p-ClC(6)H(4))}](2) was more stable than [Rh(mu-Cl)(acac)(CO)(COCOPh)](2). The reaction of p-CH(3)OC(6)H(4)COCOCl with Rh(acac)(CO)(2) did not form a similar dimeric complex as final product, but gave p-CH(3)OC(6)H(4)COCl as major product, showing thermal instability of corresponding arylglyoxyl and aroyl rhodium complexes. The reaction of C(6)F(5)CO-COCl did not form a simlar dimeric complex either, but a mononuclear complex RhCl(acac)(COCOC(6)F(5))(CO)(2) was generated as a transient intermediate, which was readily transformed to a furanone arising from reductive elimination of the acac ligand and C(6)F(5)COCO moiety followed by cyclization. In the thermolysis of [Rh(mu-Cl)(acac)(CO)(COCOAr)](2), only ArCOCl and Rh(acac)(CO)(2) were formed, and any ArCORh species could not be detected during the thermolysis process. However, the reaction of Rh(acac)(CO)(2) with PhCOCl formed RhCl(acac)(CO)(2)(COPh), albeit only to a small extent, suggesting that the reaction is not thermodynamically favored. The reaction of RhCl(CO)(PMe(3))(2) with p-ClC(6)H(4)COCOCl also proceeded cleanly to furnish p-ClC(6)H(4)COCORhCl(2)(CO)(PMe(3))(2). Thermolysis of the complex formed p-ClC(6)H(4)CORhCl(2)(CO)(PMe(3))(2), indicating slow reductive elimination of ClC(6)H(4)COCl as compared with the ArCORh species, generated in the thermolysis of [Rh(mu-Cl)(acac)(CO)(COCOAr)](2). Treatment of ClC(6)H(4)CORhCl(2)(CO)(PMe(3))(2) with carbon monoxide generates p-ClC(6)H(4)COCORhCl(2)(CO)(PMe(3))(2), although the yield was low.