[Cp*RuCl-(iPr2PNHPy)] | 1235971-00-2

• 英文名称: [Cp*RuCl-(iPr2PNHPy)]
• 英文别名: [Cp*RuCl-(ⁱPr₂PNHPy)]；[Cp*RuCl(ⁱPr₂PNHPy)]；(η5-C5Me5)RuCl(κ2-P,N-diisopropylphosphanyl(pyrid-2-yl)amine)；[Cp*RuCl(κ2P,N-P(i)Pr2NHPy)]；[(C5Me5)RuCl((i-Pr)2NHC5H4N)]
• CAS: 1235971-00-2
• 化学式: C₂₁H₃₄ClN₂PRu
• 分子量: 482.011
• InChiKey: IRUNDWFCQZUCAY-UHFFFAOYSA-M

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：

  [Cp*RuCl-(iPr2PNHPy)] 、 三甲基(对甲苯乙炔)硅烷 以 二氯甲烷 为溶剂， 以95%的产率得到[Cp*Ru=C=CH(p-C₆H₄CH₃₎(ⁱPr₂PNHPy)][Cl]
  参考文献：
  名称：

  Counteranion-Dependent Reaction Pathways in the Protonation of Cationic Ruthenium–Vinylidene Complexes

  摘要：

  The tetraphenylborate salts of the cationic vinylidene complexes (Cp*Ru=C=CHR((Pr2PNHPy)-Pr-i)](+) (R = p-C6H4CF3 (1a-BPh4), Ph (1b-BPh4), p-C6H4CH3 (1c-BPh4), p-C6H4Br (1d-BPh4), Bu-t (1e-BPh4), H (1f-BPh4)) have been protonated using an excess of HBF4 center dot OEt2 in CD2Cl2, furnishing the dicationic carbyne complexes [Cp*Ru CCH2R((Pr2PNHPy)-Pr-i)](2+) (R = p-C6H4CF3 (2a), Ph (2b), p-C6H4CH3 (2c), p-C6H4Br (2d), Bu-t (2e), H (21)), which were characterized in solution at low temperature by NMR spectroscopy. The corresponding reaction of the chloride salts 1a-Cl, 1b-Cl, 1c-Cl, and 1d-Cl followed a different pathway, instead affording the novel alkene complexes [Cp*RuCl(kappa(1)(N),eta(2)(C,C)-C5H4N-(NHPPr2CH)-Pr-i=CHR)][BF4] (3a-d). In these species, the entering proton is located at the alpha-carbon atom of the former vinylidene ligand, which also forms a P C bond with the phosphorus atom of the (Pr2PNHPy)-Pr-i ligand. To shed light on the reaction mechanism, DFT calculations have been performed by considering several protonation sites. The computational results suggest metal protonation followed by insertion. The coordination of chloride to ruthenium leads to alkenyl species which can undergo a P C coupling to yield the corresponding alkene complexes. The noncoordinating nature of [BPh4](-) does not allow the stabilization of the unsaturated species coming from the insertion step, thus preventing this alternative pathway.

  DOI：

  10.1021/om500179x
• 作为产物：
  描述：

  chloro(pentamethylcyclopentadienyl)ruthenium(II) tetramer 、 2-pyridineaminodiisopropylphosphine 以 petroleum ether 为溶剂， 以90%的产率得到[Cp*RuCl-(iPr2PNHPy)]
  参考文献：
  名称：

  带有磷酰基-吡啶配体的半夹心亚苄基钌配合物：对亲核试剂和亲电试剂的反应性

  摘要：

  螯合半稳定膦酰基-吡啶 PiPr 2 XC 5 -H 4 N（X = NH，先前描述的二异丙基膦酰基-吡啶-2-基胺，1a；X = S，新型二异丙基膦酰基巯基吡啶，1b）已被制备用作配体在合成新的半夹心氯络合物 [Ru(η 5 -C 5 Me 5 )(κ 2 -P,N-PiPr 2 XC 5 H 4 N)Cl] (X = NH, 2a; S, 2b ）。这些通用的起始化合物与苯基重氮甲烷反应生成新型卡宾钌配合物 [Ru(η 5 -C 5 Me 5 )(κ 2 -P,N-PiPr 2 XC 5 H 4 N)-(=CHC 6 H 5 )] [BAr' 4 ] (Ar' = 3,5-C 6 H 3 (CF 3 ) 2 ；X = NH，3a；S 3b)；图 3a 已通过 X 射线晶体学表征。化合物 3a 作为布朗斯台德碱与过量的三氟甲磺酸反应生成 [Ru(η 5 -C 5 Me 5 )(κ 2 -P

  DOI：

  10.1002/ejic.200901162

文献信息

• Nucleophilic Addition Reactions to Allenylidene Complexes of Ruthenium Bearing Hemilabile P,N Ligands: Isolation of the Vinylcarbene Complex [Cp*Ru═CHCH═CPh₂(ⁱPr₂PNHPy)][PF₆]
  作者：Iqbal Hyder、Manuel Jiménez-Tenorio、M. Carmen Puerta、Pedro Valerga

  DOI：10.1021/om101013j

  日期：2011.2.28

  The complex [Cp*Ru═C═C═CPh2(iPr2PNHPy)][PF6] (2), prepared by reaction of [Cp*Ru(MeCN)(iPr2PNHPy)][PF6] (1) with HC≡CC(OH)Ph2, reacts with primary amines, furnishing the corresponding vinylaminocarbenes, which are better formulated as the azoniabutadienyl derivatives [Cp*RuC(NHR)CH═CPh2}(iPr2PNHPy)][PF6] (R = Cy (6a), Me (6b), CH2C≡CH (6c)). These species result from the nucleophilic attack of the

  复杂的[CP *Ru═C═C═CPh 2（我镨2 PNHPy）] [PF 6 ]（2）中，由反应制备的[CP *茹（MeCN中）（我镨2 PNHPy）] [PF 6 ] （1）配有HC≡CC（OH）PH 2，与伯胺，家具相应vinylaminocarbenes，其被配制更好作为azoniabutadienyl衍生物的[CP *孺C（NHR）CH═CPh发生反应2 }（我镨2 PNHPy ）] [PF 6 ]（R =成分Cy（图6a）中，Me（图6b），CH 2 C≡CH（6C））。这些物质是由于胺在亚烯基配体的Cα原子上的亲核攻击而产生的。在与此变化，反应2与环状仲胺如哌啶，吡咯烷，和吗啉产生了施罗克型vinylcarbene复杂的[CP *Ru═CHCH═CPh 2（我镨2 PNHPy）] [PF 6 ]（7），这已经通过X射线结构分析得到了明确的表征。此vinylcarbene复杂据
• Counteranion and Solvent Assistance in Ruthenium-Mediated Alkyne to Vinylidene Isomerizations
  作者：Manuel Jiménez-Tenorio、M. Carmen Puerta、Pedro Valerga、Manuel A. Ortuño、Gregori Ujaque、Agustí Lledós

  DOI：10.1021/ic401119p

  日期：2013.8.5

  respective vinylidene isomers in dichloromethane is very slow and requires hours to its completion. However, this process is accelerated by addition of LiCl in methanol solution. Reaction of 1 with HC≡CR (R = COOMe, C6H4CF3) in MeOH goes through the intermediacy of the π-alkyne complexes [Cp*Ru(η2-HC≡CR)(iPr2PNHPy)]Cl (R = COOMe (3a-Cl), C6H4CF3 (3b-Cl)), which rearrange to vinylidenes in minutes,

  络合物[Cp * RuCl（i Pr 2 PNHPy）]（1）在二氯甲烷中与1-炔烃HC≡CR（R = COOMe，C 6 H 4 CF 3）反应，得到相应的亚乙烯基络合物[Cp *Ru═C═ CHR（i Pr 2 PNHPy）] Cl（R = COOMe（2a-Cl），C 6 H 4 CF 3（2b-Cl）），而1与NaBPh 4在MeOH中反应，然后加入HC≡CR（R = COOMe，C 6 H ^ 4 CF 3）得到亚稳定的π络合物炔的[Cp *茹（η 2-HC ＝ CR）（i Pr 2 PNHPy）] [BPh 4 ]（R ＝ COOMe（3a-BPh 4），C 6 H 4 CF 3 （3b-BPh 4））。的变换图3a-BPH 4 / 3B-BPH 4到在二氯甲烷它们各自的异构体亚乙烯基是很慢的，并且需要小时至其完成。但是，通过在甲醇溶液中添加LiCl可以加快此过程。的反应1与HC≡CR（R
• Internal Alkyne Isomerization to Vinylidene versus Stable π-Alkyne: Theoretical and Experimental Study on the Divergence of Analogous Cp*Ru and TpRu Systems
  作者：Vinay K. Singh、Emilio Bustelo、Isaac de los Ríos、Ignacio Macías-Arce、M. Carmen Puerta、Pedro Valerga、Manuel Ángel Ortuño、Gregori Ujaque、Agustí Lledós

  DOI：10.1021/om200273v

  日期：2011.8.8

  The activation of internal alkynes by Cp*Ru and TpRu complexes gives respectively pi-allyne and disubstituted vinylidene as stable species, even though both systems bear identical pyridylphosphine ligands (kappa P-2,N- (Pr2PXPy)-Pr-i, X = NH, CH2, S). The activation of the alkynones PhC CCOR (R = Me, Ph) by [TpRuCl((Pr2PXPy)-Pr-i)] complexes allowed us to isolate and characterize metastable eta(1)-O=C(R)C CPh adducts. These complexes isomerize spontaneously to vinylidene both in solution and in the solid state. Kinetic studies have been carried out in solution by P-31H-1} NMR and in the solid state by IR spectroscopy, providing the Eyring and Avrami-Erofeev parameters, respectively. The activation of internal alkynes without ketone groups provided vinylidene species as well, but without isolable intermediates. In contrast with the TpRu system, the activation of alkynones by [Cp*RuCl((Pr2PXPy)-Pr-1)] always results in stable pi-alkyne species. Representatives of both Cp*Ru-pi-alkyne; and TpRu-vinylidene compounds have been characterized by X-ray diffraction. DFT calculations have been carried out with the actual experimental complexes, including solvent effects, in order to analyze the mechanism of the pi-alkyne to vinylidene isomerization Of internal alkynes and to explain the divergent results obtained for Tp and Cp*.