[(η(5)-C5H5)Ru(C(OH)CH=CPh2)(CO)(PiPr3)]BF4 | 178325-75-2

• 英文名称: [(η(5)-C5H5)Ru(C(OH)CH=CPh2)(CO)(PiPr3)]BF4
• CAS: 178325-75-2
• 化学式: BF₄*C₃₀H₃₈O₂PRu
• 分子量: 649.479
• InChiKey: DBDVQWNOVDPBQN-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) 、 水 以 四氢呋喃 为溶剂， 以78%的产率得到[(η(5)-C5H5)Ru(C(OH)CH=CPh2)(CO)(PiPr3)]BF4
  参考文献：
  名称：

  Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

  摘要：

  The five-coordinate complex [RuHCl(CO)(PPr3i)(2)] (1) reacts with cyclopentadiene in methanol under reflux to give [RuH(eta(5)-C5H5)(CO)(PPr3i)] (2) and [HPPr3i]Cl. The protonation of 2 in dichloromethane-d(2) leads to the dihydrogen complex [Ru(eta(5)-C5H5)(eta(2)-H-2)(CO)(PPr3i)]BF4 (3) in equilibrium with traces of the dihydrido tautomer [RuH2(eta(5)-C5H5)(CO)(PPr3i)]BF4 (4). The reaction of 2 with HBF4 . Et(2)O in acetone affords the solvated complex [Ru(eta(5)-C5H5)(CO){eta(1)-OC(CH3)(2)}(PPr3i)]BF4 (5), which reacts with CO, dimethyl acetylenedicarboxylate, and NaCl to give [Ru(eta(5)-C5H5)(CO)(2)(PPr3i)]BF4 (6), [Ru(eta(5)-C5H5){eta(2)-C-2(CO2CH3)(2)}(CO)(PPr3i)]BF4 (7), and [Ru(eta(5)-C5H5)Cl(CO)(PPr3i)] (8), respectively, Complex 5 also reacts with alkyn-1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(eta(5)-C5H5)(C=C=CPh(2))(CO)(PPr3i)]BF4 (9), which affords [Ru(eta(5)-C5H5){C(OH)CH=CPh(2)}(CO)(PPr3i)]BF4 (10) by reaction with water. 10 is converted into the acyl derivative [Ru(eta(5)-C5H5){C(O)CH=CPh(2)}(CO)(PPr3i)] (11), when a CH2Cl2 solution of 10 is passed through an Al2O3 column. The structure of 11 was determined by an X-ray investigation. The reaction of 5 with 2-propyn-1-ol leads to the alpha,beta-unsaturated hydroxycarbene complex [Ru(eta(5)-C5H5){C(OH)CH=CH2}(CO)(PPr3i)]BF4 (12). Similarly to 10, 12 is converted into [Ru(eta(5)-C5H5){C(O)CH=CH2}(CO)(PPr3i)] (13), when the solutions of 12 are passed through an Al2O3 column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of organometallic compounds including [Ru(eta(5)-C5H5){C(OH)CH=C(CH2)(4)CH2}(CO)(PPr3i)]BF4 (14). Chromatography of the mixture affords [Ru(eta(5)-C5H5){C(O)CH=C(CH2)(4)(CH2}(CO)(PPr3i)] (15) and [Ru(eta(5)-C5H5){C=CC=CH(CH2)(3)CH2}(CO)(PPr3i)] (16). 9 reacts with alcohols and thiols to give [Ru(eta(5)-C5H5){C(ER)CH=CPh(2)}(CO)(PPr3i)]BF4 (ER = OMe (17), OEt (18), SPrn (21)), which by treatment with NaOMe afford [Ru(eta(5)-C5H5){C(ER)=C=CPh(2)}(CO)(PPr3i)] (ER = OMe (19), OEt (20), SPrn (22)).Similarly, the reaction of 9 with benzophenone imine leads to [Ru(eta(5)-C5H5){C(CH=CPh(2))=N=CPh(2)}(CO)(PPr3i)]BF4 (23), which by reaction with NaOMe gives [Ru(eta(5)-C5H5){C(N=CPh(2))=C=CPh(2)}(CO)(PPr3i)] (24). The structure of 23 was also determined by an X-ray investigation. The C=N bond lengths are 1.283(9) and 1.252(9) Angstrom, while the C-N-C angle is 149.9(6)degrees.

  DOI：

  10.1021/om960124d