CpMe₅(dppp)RuCN | 204455-59-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: CpMe₅(dppp)RuCN
• 英文别名: (pentamethylcyclopentadiene)(1,3-bis(diphenylphosphino)propane)RuCN；[Ru(η5-pentamethylcyclopentadienyl)(dppp)(CN)]；[Ru(η5-pentamethylcyclopentadienyl)(1,3-bis(diphenylphosphino)propane)(CN)]；3-diphenylphosphanylpropyl(diphenyl)phosphane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+);cyanide
• CAS: 204455-59-4
• 化学式: C₃₈H₄₁NP₂Ru
• 分子量: 674.768
• InChiKey: RFELSPMAQPKSFW-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：

  CpMe₅(dppp)RuCN 、 三氟甲磺酸 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Cyanide Ligand Basicities in Cp‘M(L)₂CN Complexes (M = Ru, Fe). Correlation between Heats of Protonation and νCN

  摘要：

  Basicities of the cyanide ligands in a series of Cp'M(L)(2)CN complexes were investigated by measuring their heats of protonation (-Delta N-CNH) by CF3SO3H in 1,2-dichloroethane solution at 25.0 degrees C to give Cp'M(L)(2)(CNH)+CF3SO3-, in which the N-H+ group is probably hydrogen-bonded o the CF3SO3- anion. Basicities (-Delta H-CNH) Of the CpRu(PR3)(2)CN complexes increase from 20.5 (PPh3) to 22.4 (PMe3) kcal/mol with increasing donor abilities of the phosphine ligands. Basicities of all the Cp'Ru(PR3)(2)CN complexes, where Cp' Cp or Cp*, are linearly correlated with their nu CN values; the nonphosphine complexes, CpRu(1,10-phen)CN and CpRu(COD)CN, do not follow the same correlation. For a large number of Cp'M(L)(2)CN complexes (M = Ru, Fe, L-2 = mono- and bidentate phosphines, CO, 1,10-phen, and COD), their nu CN values parallel nu CN values of their protonated Cp'M(L)(2)(CNH)(+) analogues. Also, P-31 NMR chemical shifts of the unprotonated Cp'M(PR3)(2)CN and protonated CpM(PR3)(2)(CNH)(+) complexes are linearly related. Despite the high basicity of Ru in Cp*Ru(PMe3)(2)Cl (30.2 kcal/mol), the CN-in Cp*Ru(PMe3)(2)CN (25.0 kcal/mol) is the site of protonation; factors that determine whether protonation occurs at the Ru or the CN- are discussed.

  DOI：

  10.1021/ic971124o
• 作为产物：
  描述：

  在 diphenylguanidine 作用下， 以 not given 为溶剂， 生成 CpMe₅(dppp)RuCN
  参考文献：
  名称：

  Cyanide Ligand Basicities in Cp‘M(L)₂CN Complexes (M = Ru, Fe). Correlation between Heats of Protonation and νCN

  摘要：

  Basicities of the cyanide ligands in a series of Cp'M(L)(2)CN complexes were investigated by measuring their heats of protonation (-Delta N-CNH) by CF3SO3H in 1,2-dichloroethane solution at 25.0 degrees C to give Cp'M(L)(2)(CNH)+CF3SO3-, in which the N-H+ group is probably hydrogen-bonded o the CF3SO3- anion. Basicities (-Delta H-CNH) Of the CpRu(PR3)(2)CN complexes increase from 20.5 (PPh3) to 22.4 (PMe3) kcal/mol with increasing donor abilities of the phosphine ligands. Basicities of all the Cp'Ru(PR3)(2)CN complexes, where Cp' Cp or Cp*, are linearly correlated with their nu CN values; the nonphosphine complexes, CpRu(1,10-phen)CN and CpRu(COD)CN, do not follow the same correlation. For a large number of Cp'M(L)(2)CN complexes (M = Ru, Fe, L-2 = mono- and bidentate phosphines, CO, 1,10-phen, and COD), their nu CN values parallel nu CN values of their protonated Cp'M(L)(2)(CNH)(+) analogues. Also, P-31 NMR chemical shifts of the unprotonated Cp'M(PR3)(2)CN and protonated CpM(PR3)(2)(CNH)(+) complexes are linearly related. Despite the high basicity of Ru in Cp*Ru(PMe3)(2)Cl (30.2 kcal/mol), the CN-in Cp*Ru(PMe3)(2)CN (25.0 kcal/mol) is the site of protonation; factors that determine whether protonation occurs at the Ru or the CN- are discussed.

  DOI：

  10.1021/ic971124o

文献信息

• Preparation of Ruthenium Azirinyl Complexes and Reversed Regiospecificity of the Carbonyl Insertion Reaction
  作者：Yih-Hsing Lo、Sheng-Cheng Hsu、Shou-Ling Huang、Ying-Chih Lin、Yi-Hong Liu、Yu Wang

  DOI：10.1021/om049528t

  日期：2004.12.1

  °C. Reaction of the methyl isocyanoacetate complex [Ru]C⋮NCH2COOMe}X (2d) with n-Bu4NOH causes hydrolysis of the ester group to give the ruthenium oxazolone complex 4d. The insertion of the CO group of acetone, aldehyde, ester, and amide into the C−C bond of the three-membered azirinyl ring of 3a−c yields a variety of five-membered oxazolinyl complexes 5−7. The regiospecificity of the insertion differs

  向[Ru] CN（1； [Ru] = Cp（PPh 3）2 Ru）进行有机卤化物的亲电加成，得到阳离子异氰酸酯络合物[CNCNCH 2 R} X（R = CN，2a ; R = CH CH 2，图2b ; R = PH，图2c），其与碱（反应ñ -Bu 4 NOH或ñ -Bu 4 NF），得到3元环azirinyl络合物。对于具有3c苯基的叠氮基络合物，将三个异构体指定为钌2 H-和1 H-azirinyl配合物，在-20°C下观察到。异氰基乙酸甲酯络合物RuC⋮NCH 2 COOMe} X（2d）与n- Bu 4 NOH的反应引起酯基的水解，得到钌恶唑酮络合物4d。的C的插入O基丙酮，醛，酯和酰胺的成的三个元azirinyl环的C-C键3A - Ç产生各种五元恶唑啉络合物5 - 7。插入的区域特异性不同于在有机叠氮系统中光化学诱导的羰基插入中观察到的区域特异性。形成中的非对映选择性5
• Syntheses, Crystal Structures, and Electron Communication Properties of a Series of Class II–III Mixed-Valence Complexes
  作者：Jin-Hui Fu、Yong He、Ying Song、Bing-Chang Tan、Xiao-Lin Liu、Yi Li、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1021/acs.cgd.4c00417

  日期：2024.8.7

  to IR spectra and crystallographic data. The mixed-valence complexes 13+–43+ show different degrees of electron delocalization and can be classified as Class II–III mixed-valence complexes, as evidenced by the NIR spectra, supported by (TD)DFT calculations. Moreover, variable-temperature electron paramagnetic resonance (EPR) spectra of the mixed-valence species show that 13+ and 23+ are localized and

  II-III类混合价物种因其在II类到III类过渡中的边界行为而引起了极大的关注。为了进一步研究这些物种，一系列含有氰化物作为桥的双核和三核配合物，[CpMe x (dppp)RuCNRu(dmap) 5 ][PF 6 ] n ( x = 0, n = 2 and 3, 1 n + ; x = 5, n = 2 和 3, 2 n + ; CpMe x = 聚甲基环戊二烯基 = 1,3-双(二苯基膦基)丙烷; dmap = 4-二甲氨基-吡啶) 和 [CpMe x (dppp)Ru–CNRu(dmap) 4 NCRu(dppp)CpMe x ][PF 6 ] n ( x = 0, n = 2 和 3, 3 n + ; x = 5, n = 2 和 3, 4 n + )，使用电化学和光谱方法以及单晶分析进行合成和表征。根据红外光谱和晶体学数据，对于所有中性物质，第一次氧化发生在氰化物的 N 配位