chloro(hydridotris(pyrazolyl)borate-N,N',N'')(phenylethynyl-κC)(triphenylphosphine)ruthenium | 184840-11-7

• 英文名称: chloro(hydridotris(pyrazolyl)borate-N,N',N'')(phenylethynyl-κC)(triphenylphosphine)ruthenium
• 英文别名: [(hydridotris(pyrazolyl)borate)RuCl(PPh3)(CCH(phenyl))]；(tris(pyrazolyl)borate)Ru(P(C6H5)3)Cl(CCH(C6H5))
• CAS: 184840-11-7
• 化学式: C₃₅H₃₁BClN₆PRu
• 分子量: 713.979
• InChiKey: WTWZRBNMIHTOJS-UHFFFAOYSA-M

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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  chloro(hydridotris(pyrazolyl)borate-N,N',N'')(phenylethynyl-κC)(triphenylphosphine)ruthenium 、 三甲基膦 以 苯 为溶剂， 以57%的产率得到[(hydridotris(pyrazolyl)borate)RuCl(PMe3)(PPh3)]
  参考文献：
  名称：

  Ruthenium(II) tris(pyrazolyl)borate complexes.† Reversible vinylidene complex formation

  摘要：

  通过中间体[Ru{HB(pz)3}Cl(PPh3)(CCHR)]（pz =Â吡唑基；R =ÂPh、SiMe3、Bun、But、CO2Et 或 C6H9）发现了一条方便的高产路线，该路线已通过晶体学表征。在沸腾的 dmf 中用 1 个等量的 PPh3 处理 [Ru{HB(pz)3}Cl(cod)]（cod =  环辛烷-1,5-二烯）时，很容易得到这种复合物。Ru{HB(pz)3}Cl(PPh3)(CCHR)] 复合物中的亚乙烯基非常容易被亲核物 L = PMe3、PPh3、MeCN、吡啶或 CO 取代，从而得到 [Ru{HB(pz)3}Cl(PPh3)L]。除了 L = PMe3 或 CO 外，这些反应都是可逆的。复合物 [Ru{HB(pz)3}Cl(PPh3)(CO)]已通过 X 射线晶体学鉴定。用过量的 HCCRâ²（Râ²Â = SiMe3、Bun、But、CO2Et 或 C6H9）处理 [Ru{HB(pz)3}Cl(PPh3)(CCHPh)] 时，可逆地形成中性亚乙烯基络合物 [Ru{HB(pz)3}Cl(PPh3)(CCHRâ²)]。通过比较研究和扩展-H¼ckel 分子轨道计算，阐明了各种亚乙烯基络合物中键合的性质。金属中心与亚乙烯基配体之间的键合主要由 dyz（金属）-p（亚乙烯基）相互作用所主导。如果这种作用很小，就可以将亚乙烯基配合物重新转化为δ-2-炔配合物。

  DOI：

  10.1039/a702194a
• 作为产物：
  描述：

  (hydrotris(pyrazol-1-yl)borato)bis(triphenylphosphane)chlororuthenium(II) 、 苯乙炔 以 四氢呋喃 为溶剂， 以92%的产率得到chloro(hydridotris(pyrazolyl)borate-N,N',N'')(phenylethynyl-κC)(triphenylphosphine)ruthenium
  参考文献：
  名称：

  中性亚乙烯基配合物引发的钌催化末端炔烃的二聚

  摘要：

  RuTp（PPh 3）2 Cl（1）和RuTp（PPh 3）（py）Cl（2）络合物催化HC⋮CR的二聚化，其中R = Ph，SiMe 3，n -Bu和t -Bu，得到的1，4-和2，4-二取代的丁炔，其转化率和选择性都强烈取决于炔烃取代基，其中催化前体是中性亚乙烯基络合物RuTp（PPh 3）（Cl）（= C CHR）。氢化物络合物RuTp（PPh 3）2 H（3）表现出与1和2相同的催化活性。

  DOI：

  10.1021/om9607816

文献信息

• A comparison of Cp*- and Tp-ruthenium carbyne complexes prepared via site selective electrophilic addition to neutral ruthenium vinylidenes
  作者：Nicholas J. Beach、Andrew E. Williamson、Gregory J. Spivak

  DOI：10.1016/j.jorganchem.2005.07.040

  日期：2005.11

  The synthesis and characterization of a series of ruthenium carbyne complexes supported by either pentamethylcyclopentadienyl (Cp*) or hydridotris(pyrazolyl)borate (Tp) ligands are discussed. Reacting the neutral ruthenium(II) vinylidenes [Cp*Cl(PPh3)Ru(CCHR)] (1) or [TpCl(PPh3)Ru(CCHR)] (2) with excess HBF4 · Et2O yields the ruthenium(IV) carbynes [Cp*Cl(PPh3)Ru(CCH2R)][BF4] (3: R = tBu, 3a; R = nBu

  讨论了五甲基环戊二烯基（Cp *）或氢化三（吡唑基）硼酸酯（Tp）配体负载的一系列钌卡宾配合物的合成和表征。使中性钌（II）亚乙烯基[Cp * Cl（PPh 3）Ru（CCHR）]（1）或[TpCl（PPh 3）Ru（CCHR）]（2）与过量的HBF 4  ·Et 2 O反应生成钌（IV）卡宾[Cp * Cl（PPh 3）Ru（CCH 2 R）] [BF 4 ]（3：R =  t Bu，3a ; R =  n Bu，3b ; R = Ph，3c），和[TpCl （PPh 3）Ru（CCH 2 R）] [BF 4 ]（4：R ＝  t Bu，4a； R ＝  n Bu，4b； R ＝ Ph，4c）。配合物3a和3b是可分离的固体，而3c和4a – c必须制备并在低温下使用可变温度NMR光谱在溶液中检查。相反，1或2（R = Ph）与MeOTf的反应选择性地产生氯化物抽象产物[Cp *（OTf）（PPh
• Reactivity of [TpRuCl(PTA)(PPh₃)] with Alkynes and Propargylic Alcohols: Occurrence of Structurally Related Cationic vs Neutral Allenylidene Complexes with the Ruthenium Hydrotris(pyrazolyl)borate Moiety
  作者：Sandra Bolaño、M. Mar Rodríguez-Rocha、Jorge Bravo、Jesús Castro、Enrique Oñate、Maurizio Peruzzini

  DOI：10.1021/om9005142

  日期：2009.10.26

  [TpRuCl(PTA)(PPh3)] (1; PTA = 1,3,5-triaza-7-phosphaadamantane) reacts with phenylacetylene, yielding the alkynyl complex [TpRu(C CPh)(PTA)(PPh3)] (2) or the neutral vinylidene complex [TpRuClC=C(H)Ph}(PTA)] (4), depending on the solvent and the reaction conditions (Tp = hydrotris(pyrazolyl)borate). Protonation of 2 with HOTf (OTf = OSO2CF3) in CH2Cl2 yields the dicationic vinylidene compound [TpRuC=C(H)Ph}PTAH}(PPh3)](OTf)(2) (3), bearing a N-protonated PTA ligand. Reaction of 1 with 1,1-diphenyl-2-propyn-1-ol affords the new cationic compound [TpRu(C=C=CPh2)(PTA)(PPh3)]PF6 (5) or neutral allenylidene compound [TpRuCl-(C=C =CPh2)(PTA)] (6), depending on the reaction solvent (MeOH or toluene, respectively). The reactivity of complexes 5 and 6 toward tertiary phosphines (PTA and PPh2Me) has been investigated. Remarkably, both the cationic and the neutral allenylidene compounds undergo regioselective nucleophilic attack at the allenylidene C-alpha position to give the sigma-allenyl-phosphonium complexes [TpRuC(L)=C=CPh2}(PTA)(PPh3)]PF6 (L = PPh2Me (8), PTA (9)) and [TpRuClC(L)= C=CPh2}(PTA)] (L = PTA (10), PPh2Me (11)), respectively. Noticeably, the reaction goes to completion in the case of the neutral allenylidene complex 6, whereas an equilibrium between the phosphonioallenyl adduct and the educt species is observed in the case of the cationic allenylidene compound 5. The thermodynamic parameters for such an equilibrium have been determined by NMR methods at different temperatures. Finally, the hydrolysis of the neutral allenylidene 6 has been briefly considered, showing the formation of the carbonyl compound [TpRuCl(CO)-(PTA)] (7).
• Reaction of Tp(PPh₃)Ru(η²-O₂CCHPh₂) with Carbene and Vinylidene Precursors
  作者：Melanie S. Sanford、Michelle R. Valdez、Robert H. Grubbs

  DOI：10.1021/om010558v

  日期：2001.12.1

  Tp(PPh3)Ru(eta (2)-O2CCHPh2) (1) [Tp = tris(pyrazolyl)borate] has been prepared by the reaction of TpRu(Cl)(PPh3)(2) with 1.2 equiv of NaO2CCHPh2. Complex 1 reacts with diphenylcyclopropene to generate the metallacycle Tp(PPh3)Ru[kappa (2)-(C,O)-C(double bond CHCHPh2)OC(CHPh2)double bondO] (2). A trace of the carbene Tp(PPh3)(eta (1)-O2CCHPh2)Ru double bond CHCH double bondC(Ph)(2) (3) is also observed in the crude reaction mixture. Compound I reacts with phenyldiazomethane to form the benzylidene Tp(PPh3)(eta (1)-O2CCHPh2)Ru double bond CHPh (4). A similar species is also available by the reaction between AgO2CCHPh2 and Tp(PCy3)(Cl)Ru double bond CHCH double bondC(CH3)(2) (5), which affords Tp(PCy3)(eta (1)-O2CCHPh2)Ru double bond CHCH double bondC(CH3)(2) (6). With the addition of an excess of HCl, complexes 4 and 6 release free HO2CCHPh2 and are converted to Tp(PPh3)(Cl)Ru double bond CHPh (7) and complex 5, respectively. The reaction of I with phenylacetylene yields the five-membered chelate TP(PPh3)Ru[kappa (2)-(C,O)-C(double bond CHPh)OC(CHPh2)double bondO] (8). Complex 8 is also formed in the reaction of Tp(PPh3)(Cl)Ru double bondC double bond CHPh with 1.2 equiv of AgO2CCHPh2. Compounds 1, 2, and 8 have been characterized by X-ray crystallography. Complexes 2, 5, 6, 7, and 8 do not catalyze olefin metathesis reactions, while 4 is an active initiator for the ring-opening metathesis polymerization of norbornene.