[Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P(Pr(i))3)](tetrafluoroborate) | 178325-73-0

• 英文名称: [Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P(Pr(i))3)](tetrafluoroborate)
• 英文别名: [Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P((i)Pr)3)](BF4)；[(η(5)-C5H5)Ru(C=C=CPh2)(CO)(PiPr3)]BF4；[Ru(η(5)-C5H5)(C=C=CPh2)(CO)(PiPr3)]BF4；[Ru(η(5)-C5H5)(PiPr3)(CO)(C=C=CPh2)]BF4；[Ru(η5-C5H5)(C=C=CPh2)(CO)(PPri3)]BF4；[Ru(η5-C5H5)(CCC(phenyl)2)(CO)(P(isopropyl)3)]BF4
• CAS: 178325-73-0
• 化学式: BF₄*C₃₀H₃₆OPRu
• 分子量: 631.464
• InChiKey: FHQXQSNLUNTNSD-UHFFFAOYSA-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：

  [Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P(Pr(i))3)](tetrafluoroborate) 、 丙酮 在 KOH 作用下， 以 丙酮 为溶剂， 以25%的产率得到Ru(η(5)-C5H5)(-C*C-CPh2-CH2COCH3)(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
• 作为产物：
  描述：

  [(η(5)-C5H5)Ru(CO)(η(1)-OC(CH3)2)(PiPr3)]BF4 、 1,1-二苯基-2-丙炔-1-醇 以 二氯甲烷 为溶剂， 以87%的产率得到[Ru(η(5)-C5H5)(=C=C=CPh2)(CO)(P(Pr(i))3)](tetrafluoroborate)
  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

文献信息

• C−N and C−C Coupling Reactions:  Preparation of New N-Heterocyclic Ruthenium Derivatives
  作者：María L. Buil、Miguel A. Esteruelas、Ana M. López、Enrique Oñate

  DOI：10.1021/om020652r

  日期：2003.1.1

  contrast to propargylamine, the addition of 1,1-diethylpropargylamine to 1 leads to the dihydropyridiniumyl derivative [Ru(η5-C5H5)2,2-diethyl-5-diphenylidene-2,5-dihydropyridinium-6-yl)(CO)(PiPr3)]BF4 (5) in a one-pot synthesis. Complex 1 also reacts with N-methylpropargylamine. The reaction affords [Ru(η5-C5H5)C(CHCPh2)N(CH3)CH2C⋮CH}(CO)(PiPr3)]BF4 (6). Treatment of 6 with sodium methoxide, at −78

  三种新型类型的含杂环配体配合物是通过的allenylidene配体的缩合的[Ru（η制备5 -C 5 H ^ 5）（C ^ C ^器CPh 2）（CO）（P我镨3）] BF 4（1）与炔丙基胺。复杂1起反应再与炔丙基，得到最初的[Ru（η 5 -C 5 H ^ 5）C（CH器CPh 2）NHCH 2 C ^⋮CH}（CO）（P我镨3）] BF 4（2）。治疗2，用KOH的甲醇溶液，得到双环衍生物的Ru（η 5 -C 5 H ^ 5）4-亚甲基-6,6-二苯基-2-氮杂双环[3.1.0]己-2-烯-1-基}（CO ）（P i Pr 3）（3）。形成3经由中间的Ru（η发生5 -C 5 H ^ 5）C（CH器CPh 2）NCH 2 ç⋮CH}（CO）（P我镨3）（4），其被分离时2的质子化在四氢呋喃中作为溶剂进行。相反炔丙胺，加入1,1- diethylpropargylamine至1个
• Synthesis of Novel Organometallic Compounds Containing η¹-Carbon Polycyclic Ligands:  Condensation of Propargyl Alcohol with the Allenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PPrⁱ₃)]BF₄
  作者：Miguel A. Esteruelas、Angel V. Gómez、Ana M. López、Montserrat Oliván、Enrique Oñate、Natividad Ruiz

  DOI：10.1021/om990456t

  日期：2000.1.1

  3-c]-1-furanylidene}(CO)(PPri3)]BF4 (3), which reacts with NaBH4 to give Ru(η5-C5H5)CH2(1-phenyl-3-hydroxymethyl-2-naphthyl)}(CO)(PPri3) (4). The structure of 3 was determined by an X-ray diffraction analysis, revealing a Ru−C bond length of 2.004(2) Å. Treatment of 2 with 3 equiv of NaOCH3 leads to a mixture of compounds containing the racemic form (RuR,CR;RuS,CS)-Ru(η5-C5H5)9-phenyl-1,3-dihydronaphtho[2,

  所述allenylidene复杂的[Ru（η 5 -C 5 H ^ 5）C Ç器CPh 2 }（CO）（PPR我3）] BF 4（1）反应与炔丙醇，得到α，β不饱和衍生物alkoxycarbene的[Ru （η 5 -C 5 H ^ 5）C（OCH 2 ç⋮CH）CH器CPh 2 }（CO）（PPR我3）] BF 4（2）。2的结构通过X射线研究确定，揭示Ru-C距离为1.965（4）Å。用1当量的Na处理22次CO 3，得到的[Ru（η 5 -C 5 H ^ 5）9-苯基-1,3-二氢萘并[2,3- c ^ ] -1- furanylidene}（CO）（PPR我3）] BF 4（3），其用NaBH发生反应4得到的Ru（η 5 -C 5 H ^ 5）CH 2（1-苯基-3-羟甲基-2-萘基）}（CO）（PPR我3）（4）。3的结构通过X射线衍射分析确定，揭示Ru-C键长为2.004（2）Å。用3当量的NaOCH
• 1,2,3-Diheterocyclization Reactions on the Allenylidene Ligand of a Ruthenium Complex
  作者：Miguel A. Esteruelas、Angel V. Gómez、Ana M. López、Enrique Oñate

  DOI：10.1021/om980230a

  日期：1998.8.1

  The allenylidene complex [Ru(η5-C5H5)(CCCPh2)(CO)(PPri3)]BF4 (1) reacts with pyrazole to afford (2) as a result of the addition of pyrazole to the allenylidene of 1. The structure of 2 was determined by an X-ray investigation, revealing a Ru−C(bicycle) distance of 2.073(4) Å. Treatment of 2 with sodium methoxide deprotonates the bicycle, which also undergoes an opening process to give the functionalized

  所述allenylidene复杂的[Ru（η 5 -C 5 H ^ 5）（C Ç器CPh 2）（CO）（PPR我3）] BF 4（1）反应与吡唑，得到（2）由于加入吡唑的结果到1的亚烯基。2的结构通过X射线研究确定，揭示Ru-C（自行车）距离为2.073（4）Å。用甲醇钠处理2使自行车去质子化，该自行车也经历开环过程，得到官能化的炔基衍生物（3）。1的反应用3，5-二甲基吡唑和3-甲基吡唑得到（R ＝ CH 3（8），H（9））。在甲醇钠存在下，配合物9得到（10）。1的亚烯基配体还添加吡啶-2-硫醇。在这种情况下，反应产物为（11），其通过与甲醇钠反应而得到烯基衍生物（12）。
• Regioselective Addition of PRPh₂ to the C_α Atom of the Diphenylallenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PPrⁱ₃)]BF₄
  作者：Miguel A. Esteruelas、Angel V. Gómez、Ana M. López、Javier Modrego、Enrique Oñate

  DOI：10.1021/om980577d

  日期：1998.11.1

  The allenylidene ligand of [Ru(η5-C5H5)CCCPh2}(CO)(PPri3)]BF4 adds PHPh2, PMePh2, and PPh3 selectively at the Cα atom, whereas OH- and [OMe]- are added at the Cγ atom.

  的配体allenylidene的[Ru（η 5 -C 5 H ^ 5）C Ç器CPh 2 }（CO）（PPR我3）] BF 4添加PHPh 2，PMePh 2，和PPH 3选择性地在C α原子，而OH -和[OME] -是在C中加入γ原子。
• Preparation and Characterization of 4-Azoniaheptatrienyl, 4-Azaheptatrienyl, Ruthenapyrrolinone, and Pyrrolinyl Complexes of Ruthenium
  作者：María L. Buil、Miguel A. Esteruelas、Ana M. López、Enrique Oñate

  DOI：10.1021/om030518m

  日期：2003.12.1

  4-azonia-1,3,6-heptatrienyl derivative [Ru(η5-C5H5)C(CHCPh2)NH(CH2CHCH2)}(CO)(PiPr3)]BF4 (7). In contrast to 2, the deprotonation of 7 with sodium methoxide in tetrahydrofuran takes place at the nitrogen atom. In toluene at 70 °C, the resulting 4-aza-1,3,6-heptatrienyl complex Ru(η5-C5H5)C(CHCPh2)NCH2CHCH2}(CO)(PiPr3) (8) isomerizes into the conjugated 4-aza-1,3,5-heptatrienyl derivative Ru(η5-C5H5)C(CHC

  所述allenylidene复杂的[Ru（η 5 -C 5 H ^ 5）（C ^ C ^器CPh 2）（CO）（P我镨3）] BF 4（1）将二烯丙基胺得到的N-H键Ñ -allyl- 4氮鎓-1,3,6- heptatrienyl衍生物的[Ru（η 5 -C 5 H ^ 5）C（CH器CPh 2）N（CH 2 CH CH 2）2 }（CO）（P我镨3）] BF 4（2）。治疗2用甲醇钠在四氢呋喃中产生一个烯丙基的NCH 2基团去质子化，并形成1：1的钌-吡咯啉酮配合物（R Ru，R C-（3）和吡咯烷基化合物（R Ru，小号ç - （4。）的质子化4用HBF 4 ·OET 2在乙醚最初通向杂环衍生物（[R钌，小号ç - （5），含有一个C-N双键。在二氯甲烷中，复杂5是不稳定的和演进到Ñ -烯丙基-4-氮鎓- 1,3,5- heptatrienyl复杂的[Ru（η 5 -C 5 H ^