Rh(acac)(cyclooctene)(PCy3) | 178211-40-0

• 英文名称: Rh(acac)(cyclooctene)(PCy3)
• CAS: 178211-40-0
• 化学式: C₃₁H₅₄O₂PRh
• 分子量: 592.648
• InChiKey: AFQDYHWGYKTGRH-IUJXYRIYSA-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(acac)(cyclooctene)(PCy3) 以 正己烷 、 正戊烷 为溶剂， 生成 Rh((CH3CO)2CH)((E)-CH=CHPh)(P(C6H11)3)
  参考文献：
  名称：

  Synthesis of Rh(acac)H(GeEt₃)(PCy₃) and Rh(acac)H(SnPh₃)(PCy₃) and Their Reactions with Alkynes

  摘要：

  The monoolefin complex Rh(acac)(cyclooctene)(PCy(3)) (1) reacts with HGeEt(3) to give Rh(acac)fl(GeEt(3))(PCy(3)) (2). On treatment of 2 with methyl propiolate and phenylacetylene the complexes Rh(acac){eta(2)-CH(GeEt(3))=CHR}(PCy(3)) (R = CO(2)Me (3), Ph (4)) are obtained. The X-ray crystal structure analysis of 3 reveals that the coordination geometry around the rhodium center is almost square-planar with the olefin disposed perpendicular to the coordination plane of the rhodium atom. Complex 1 also reacts with HSnPh(3). The reaction leads to Rh(acac)H(SnPh(3))(PCy(3)) (5). In the presence of methyl propiolate, phenylacetylene, and (trimethylsilyl)acetylene complex 5 affords the alkenyl compounds Ph(acac){(E)-CH=CHR}(SnPh(3))(PCy(3)) (R = CO(2)Me (6), Ph (7), SiMe(3) (8)). Similarly, the reactions of 5 with diethyl acetylenedicarboxylate and diphenylacetylene yield Rh(acac)(CR=CHR)(SnPH3)(PCy(3)) (R = CO(2)Et (9), Ph(10)). The addition of 1 equiv of 1-ethynyl-1-cyclohexanol to a pentane suspension of 5 leads to the hydroxyalkenyl derivative Rh(acac)-{(E)-CH=CHC(OH)(CH2)(4)CR(2)}(SnPh(3))(PCy(3)) (11). The structure of 11 was determined by X-ray analysis. The coordination geometry around the metal center can be rationalized as a square pyramid with the stannyl ligand in the apical position, Although the hydroxyalkenyl ligand of 11 is stable and does not-dehydrate to give the corresponding alpha,beta-unsaturated alkenyl compound, complexes of this type can be prepared from enynes. Thus, the reaction of 5 with 2-methyl-1-buten-3-yne leads to the alpha,beta-unsaturated alkenyl complex Rh(acac){(E)-CH=CHC(CH3)=CH2} (SnPh(3))(PCy(3)) (12), whereas in the presence of 1,1-diphenyl-2-propyn-1-ol complex 5 affords the allenyl derivative Rh(acac)(CH=C=CPh(2))(SnPh(3))(PCy(3)) (13).

  DOI：

  10.1021/om9602926
• 作为产物：
  描述：

  顺-环辛烯 、 Rh(acac)(PCy3)(η(2)-(E)-Et3GeCH=CHC(OH)Ph2) 以 甲苯 为溶剂， 生成 (E)-Et3GeCH=CHC(OH)Ph2 、 Rh(acac)(cyclooctene)(PCy3)
  参考文献：
  名称：

  The π-(Hydroxyalkenyl)germane Complexes Rh(acac){η²-(E)-Et₃GeCHCHC(OH)R₂}(PCy₃) (R = Me, Ph) as Intermediates in the Hydrogermylation of Alkynols Catalyzed by Rh(acac)(cyclooctene)(PCy₃)

  摘要：

  The (hydroxyalkenyl)germanes (E)-R3GeCH=CHC(OH)R'(2) (R = Et, Ph; R' = Me, Ph) are prepared in quantitative yield, and in a catalytic manner, by addition of germanes to the alkynols HC=CC(OH)R'(2) (R' = Me, Ph) in the presence of the complex: Rh(acac)(cyclooctene)(PCy3). During the reactions four cycles are evident. They have as a common point the intermediates Rh(acac){eta(2)-(E)-CH(GeR3)=CHC(OH)R'(2)}(PCy3), which have been isolated for R = Et and R' = Me, Ph.

  DOI：

  10.1021/om981042n
• 作为试剂：
  描述：

  三苯基氢化锗 、 1,1-二苯基-2-丙炔-1-醇 在 Rh(acac)(cyclooctene)(PCy3) 作用下， 以 氘代苯 为溶剂， 以71%的产率得到(E)-Ph3GeCH=CHC(OH)Ph2
  参考文献：
  名称：

  The π-(Hydroxyalkenyl)germane Complexes Rh(acac){η²-(E)-Et₃GeCHCHC(OH)R₂}(PCy₃) (R = Me, Ph) as Intermediates in the Hydrogermylation of Alkynols Catalyzed by Rh(acac)(cyclooctene)(PCy₃)

  摘要：

  The (hydroxyalkenyl)germanes (E)-R3GeCH=CHC(OH)R'(2) (R = Et, Ph; R' = Me, Ph) are prepared in quantitative yield, and in a catalytic manner, by addition of germanes to the alkynols HC=CC(OH)R'(2) (R' = Me, Ph) in the presence of the complex: Rh(acac)(cyclooctene)(PCy3). During the reactions four cycles are evident. They have as a common point the intermediates Rh(acac){eta(2)-(E)-CH(GeR3)=CHC(OH)R'(2)}(PCy3), which have been isolated for R = Et and R' = Me, Ph.

  DOI：

  10.1021/om981042n

文献信息

• Reductive Elimination of [Ph₂CCCHPR₃]BF₄ from the Rhodium(III)−Allenyl Derivatives [Rh(acac){CHCCPh₂}(PR₃)₂]BF₄ (PR₃ = PCy₃, P<i>i</i>Pr₃)
  作者：Miguel A. Esteruelas、Fernando J. Lahoz、Marta Martín、Enrique Oñate、Luis A. Oro

  DOI：10.1021/om970567x

  日期：1997.10.1

  allenylphosphonium compound [Rh(acac)η2-CH(PCy3)CCPh2}(PCy3)]BF4 (7). The X-ray crystal structure analysis of 7 reveals that the coordination geometry around the rhodium center is almost square-planar with the CH(PCy3)C bond disposed perpendicular to the coordination plane of the rhodium center. The allenylphosphonium ligand of 7 is easily displaced by carbon monoxide, to give Rh(acac)(CO)(PCy3) (8) and

  配合物Rh（aCAC）（cyclooctadiene）（PR 3）（PR 3 = PCy 3（1），P i Pr 3（2））的烯烃单元被1,1-二苯基-2-丙炔-1-取代醇，得到的Rh（ACAC）η 2 -HC⋮CC（OH）PH 2 }（PR 3）（PR 3 = PCY 3（3），P我镨3（4））。在60°C下，在甲苯为溶剂中，在1当量的膦存在下，配合物3和4演化为Rh（aCAC）H C⋮CC（OH）Ph 2 }（PR3）2（PR 3 = PCy 3（5），P i Pr 3（6））。在-78℃下，的复杂治疗5用HBF 4 ·OET 2个通向allenylphosphonium化合物的[Rh（ACAC）η 2 -CH（PCY 3）c ^器CPh 2 }（PCY 3）] BF 4（7） 。对7的X射线晶体结构分析表明，铑中心周围的配位几何结构与CH（PCy 3）几乎呈正方形。垂直于铑中心