Ru(η(5)-C5H5)(-C*C-CPh2-C*CPh)(CO)(P((i)Pr)3) | 199527-88-3

• 英文名称: Ru(η(5)-C5H5)(-C*C-CPh2-C*CPh)(CO)(P((i)Pr)3)
• CAS: 199527-88-3
• 化学式: C₃₈H₄₁OPRu
• 分子量: 645.787
• InChiKey: VIFPBQIHANDUMC-UHFFFAOYSA-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：

  [Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P(Pr(i))3)](tetrafluoroborate) 、 lithium phenylacetylide 以 四氢呋喃 为溶剂， 以41%的产率得到Ru(η(5)-C5H5)(-C(=C=CPh2)-C*CPh)(CO)(P((i)Pr)3)
  参考文献：
  名称：

  Addition of Carbon Nucleophiles to the Allenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PⁱPr₃)]BF₄:  Synthesis of New Organic Ligands by Formal C−C Coupling between Mutually Inert Fragments

  摘要：

  EHT-MO Calculations on the model cation [Ru(eta(5)-C5H5)(C=C=CH2)(CO)(PH3)](+) (1a) suggest that 23% and 31% of the LUMO and 26% of the HOMO of [Ru(eta(5)-C5H5)(C=C=CPh2)(CO)((PPr3)-Pr-i)]BF4 (1) are located on C-alpha, C-gamma, and C-beta of the allenylidene ligand, respectively, On the basis of these results, we report a new synthetic strategy for the preparation of compounds resulting from the formal addition of phenylacetylene, acetone, and methane to the allenylidene of 1. Treatment of 1 with LiC=CPh leads to the allenyl complex Ru(eta(5)-C5H5){C(C=CPh)=C=CPh2}(CO)((PPr3)-Pr-i) (2) and the alkynyl derivative Ru(eta(5)-C5H5){C=C-C(Ph)(2)C=Cph}(Co)((PPr3)-Pr-i) (3), The reaction of 2 with HBF4 affords the substituted carbene compound [Ru(eta(5)-C5H5){C(C=CPh)CH=CPh2}(CO)((PPr3)-Pr-i)]BF4 (4), which is a result from the formal addition of phenylacetylene to the C-alpha-C-beta double bond of the allenylidene of 1, The molecular structure of 4 has been determined by X-ray crystallography. The geometry around the ruthenium center is close to octahedral with the cyclopentadienyl ligand occupying three sites of a face. The Ru=C bond length is 2.004(5) Angstrom. In the presence of KOH, complex 1 reacts with acetone to give Ru(eta(5)-C5H5){C=C-C(Ph)(2)CH2C(O)CH3}(CO)((PPr3)-Pr-i). (5). The reaction of 5 with HBF4 leads to the unsaturated cyclic carbene complex [Ru(eta(5)-C5H5){CCH2C(Ph)(2)CH=C(CH3)O}(CO)((PPr3)-Pr-i)]BF4 (6). Complex 5 also reacts with 2 equiv of CF3-CO2D to give [Ru(eta(5)-C5H5){CCD2C(Ph)(2)CH=C(CH3)O}(CO)((PPr3)-Pr-i)](CF3CO2) (6-d(2)) and CF3CO2H, and the reaction of Ru(eta(5)-C5H5){C=C-C(Ph)(2)CD2C(O)CD3}(CO)((PPr3)-Pr-i) (5-d(5)) with 2 equiv of HBF4 affords [Ru(eta(5)-C5H5){CCH2C(Ph)(2)CD=C(CD3)O}(CO)((PPr3)-Pr-i)]BF4 (6-d(4)) and DBF4.On the basis of these isotope labeling experiments, the mechanism for the addition of acetone to the allenylidene Ligand of 1 is discussed, Complex 1 also reacts with Na(acac) and CH3Li. The reaction with Na(acac) leads to Ru(eta(5)-C5H5){C=C-C(Ph)(2)CH[C(O)CH3](2)}(CO)((PPr3)-Pr-i) (7), while the treatment of 1 with CH3Li gives a mixture of Ru(eta(5)-C5H5){C(CH3)=C=CPh2}(CO)((PPr3)-Pr-i) (8) and Ru(eta(5)-C5H5){C=C-C(Ph)(2)CH3}(CO)((PPr3)-Pr-i) (9). Complex 9 reacts with HBF4 to afford [Ru(eta(5)-C5H5){C=CHC(Ph)(2)CH3}(CO)((PPr3)-Pr-i)]BF4 (10), which is a result of the formal addition of a C-H bond of methane to the C-beta-C-gamma double bond of the allenylidene of 1.

  DOI：

  10.1021/om9708539