Cp(1,3-bis(diphenylphosphino)propane)RuCN | 204455-61-8

• 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: Cp(1,3-bis(diphenylphosphino)propane)RuCN
• 英文别名: Cp(dppp)RuCN；cyclopenta-1,3-diene;3-diphenylphosphanylpropyl(diphenyl)phosphane;ruthenium(2+);cyanide
• CAS: 204455-61-8
• 化学式: C₃₃H₃₁NP₂Ru
• 分子量: 604.633
• InChiKey: OZFHXENBBUVRRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.14
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Cp(1,3-bis(diphenylphosphino)propane)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 Cp(1,3-bis(diphenylphosphino)propane)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

• 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