[Rh(μ-Cl)(acetylacetonate)(CO)(COCOC6H5)]2 | 1260180-51-5

• 英文名称: [Rh(μ-Cl)(acetylacetonate)(CO)(COCOC6H5)]2
• CAS: 1260180-51-5
• 化学式: C₂₈H₂₄Cl₂O₁₀Rh₂
• 分子量: 797.21
• InChiKey: OPZWRZOZZLXFLW-UHFFFAOYSA-L

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(μ-Cl)(acetylacetonate)(CO)(COCOC6H5)]2 以 氘代苯 为溶剂， 生成 acetylacetonatodicarbonylrhodium(l)
  参考文献：
  名称：

  Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

  摘要：

  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.

  DOI：

  10.1021/om101079e
• 作为产物：
  描述：

  氧代(苯基)乙酰氯 、 acetylacetonatodicarbonylrhodium(l) 以 甲苯 为溶剂， 以76%的产率得到[Rh(μ-Cl)(acetylacetonate)(CO)(COCOC6H5)]2
  参考文献：
  名称：

  Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

  摘要：

  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.

  DOI：

  10.1021/om101079e