Cp*Ru(1,2-bis(diphenylphosphino)ethane)CN | 204455-50-5

• 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*Ru(1,2-bis(diphenylphosphino)ethane)CN
• 英文别名: Cp*Ru(dppe)CN；Cp*Ru^II(dppe)CN；CpMe₅(dppe)RuCN；CpMe₅(1,2-bis-(diphenylphosphino)ethane)RuCN；[Ru(CN)(1,2-bis(diphenylphosphino)ethane)(η5-C5Me5)]；[Ru(CN)(dppe)Cp*]；2-diphenylphosphanylethyl(diphenyl)phosphane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+);cyanide
• CAS: 204455-50-5
• 化学式: C₃₇H₃₉NP₂Ru
• 分子量: 660.741
• InChiKey: MCJZIRLKAULVJP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.29
• 重原子数：
  41
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 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*Ru(1,2-bis(diphenylphosphino)ethane)CN 、 三氟甲磺酸 以 二氯甲烷 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*Ru(1,2-bis(diphenylphosphino)ethane)CN
  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

• Different Degrees of Electron Delocalization in Mixed Valence Ru-Ru-Ru Compounds by Cyanido-/Isocyanido-Bridge Isomerism
  作者：Yu-Ying Yang、Xiao-Quan Zhu、Sheng-Min Hu、Shao-Dong Su、Lin-Tao Zhang、Yue-Hong Wen、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1002/anie.201806157

  日期：2018.10.22

  characterized. 13+[PF6]3 and 23+[PF6]3 are the one‐electron oxidation products of 12+[PF6]2 and 22+[PF6]2, respectively. The results suggest that 1[PF6]3 is a class III mixed valence compound, whereas 2[PF6]3 might be an unusually symmetrical class II–III mixed valence compound composed of the two asymmetrical delocalized RuIII−NC−RuII mixed valence subunits.

  三金属化合物的两种稳定的对反式的[Cp *（DPPE）的Ru（μ-NC）的Ru（DMAP） - 4（μ-CN）的Ru（DPPE）的Cp *] [PF 6 ] Ñ（1 [PF 6 ] Ñ，n = 2，3; Cp * = 1,2,3,4,5-戊甲基环戊二烯; DPPE = 1,2-双-（二苯基膦基）乙烷; DMAP = 4-二甲基氨基吡啶）和反式-[Cp *（DPPE） Ru（μ-CN）Ru（DMAP）4（μ-NC）Ru（DPPE）Cp *] [PF 6 ] n（2 [PF 6 ] n，n = 2，3），表明存在氰化物/异氰化物异构体，已经合成并充分表征。1个3+ [PF 6 ] 3和2 3+ [PF 6 ] 3分别是1 2+ [PF 6 ] 2和2 2+ [PF 6 ] 2的单电子氧化产物。结果表明1 [PF 6 ] 3是III类混合价化合物，而2 [PF 6 ] 3可能是由两个不对称离域的Ru
• The MMCT excited state of a localized mixed valence cyanido-bridged Ru^II–RuIII,III2–Ru^II complex
  作者：Shao-Dong Su、Xiao-Quan Zhu、Lin-Tao Zhang、Yu-Ying Yang、Yue-Hong Wen、Xin-Tao Wu、Song-Qiu Yang、Tian-Lu Sheng

  DOI：10.1039/c9dt01503e

  日期：——

  reveals that the MMCT rate of 1 and 2 is 0.18 × 1014 s−1 (τ = 5.7 × 10−14 s) and 0.29 × 1013 s−1 (τ = 3.46 × 10−13 s), respectively, which suggests that the MMCT rate or the lifetime of the MMCT excited state may be controlled by a slight change of the substituent group on the metal center.

  为了研究MV络合物的MMCT激发态，设计并合成了两个对称的四核氰基桥联的局部MV络合物Ru II CNRu III，III 2 NCRu II。超快速时间分辨瞬态吸收（TA）光谱实验表明，1和2的MMCT速率分别为0.18×10 14 s -1（τ = 5.7×10 -14 s）和0.29×10 13 s -1（τ = 3.46×10 -13 s），分别表明MMCT速率或MMCT激发态的寿命可以通过金属中心上取代基的轻微变化来控制。
• Influence of donor and acceptor substitution on the MMCT properties of binuclear cyanide bridged Schiff base compounds
  作者：Zi-Qin Wei、Qing-Dou Xu、Yang Liu、Ying-Ying Huang、Yi Li、Xiao-Lin Liu、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1016/j.poly.2021.115639

  日期：2022.2

  series of compounds, decreasing the electron donating ability of the ligand on the acceptor fragment or increasing the electron donating ability of the ligand on the donor fragment is conducive to MMCT; for the Ru-Fe series of compounds, with the enhancement of the electron donating ability of the ligand on the donor fragment, the energy of the MMCT decreases gradually; from the Fe-Fe series of compounds

  为了探索配体的给电子能力对金属到金属电荷转移 (MMCT) 的受体和供体碎片的影响，一系列不对称双金属氰化物桥接配合物 [L 1 Fe(NC)Y(dppe) L 2 ][CF 3 SO 3 ] (Y = Fe, L 1  = saldien, L 2  = Cp, 1 ; Y = Fe, L 1  = Cl 2 (saldien), L 2  = Cp 2 ; Y = Fe, L 1 = (NO 2 ) 2 (saldien), L 2  = Cp, 3 ; Y = Fe, L 1 = (NO 2 )2 (saldien), L 2  = Cp 5 , 4 ; Y = Ru, L 1 = (NO 2 ) 2 (saldien), L 2  = Cp, 5；Y = Ru，L 1 = (NO 2 ) 2 (saldien)，L 2  = Cp 5 , 6；saldien = 4-azaheptamethylene-1
• Influence of the electronic effect of an ancillary ligand on MMCT and LMCT in localized cyanide-bridged complexes containing non-innocent ligands
  作者：Yong He、Ying-Ying Huang、Jin-Hui Fu、Yang Liu、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1039/d2dt03048a

  日期：——

  Mixed-valence (MV) complexes containing non-innocent ligands are excellent models for the investigation of the electron-transfer process. A series of twelve bimetallic cyanide-bridged complexes [CpMen(dppe)RuCNFeLx][A] (A = PF6− or I−, CpMen = alkyl cyclopentadienyl, dppe = 1,2-bis (diphenylphosphino)ethane, and LX = pentane-2,4-dione-bis (S-alkylisothiosemi-carbazonato); n = 0, x = Methyl (Me), Ethyl

  含有非无辜配体的混合价 (MV) 配合物是研究电子转移过程的优秀模型。一系列十二种双金属氰化物桥联络合物[CpMe n (dppe)RuCNFeL x ][A]（A = PF 6 -或 I -，CpMe n = 烷基环戊二烯基，dppe = 1,2-双（二苯基膦基）乙烷，和L X = 戊烷-2,4-二酮-双（S-烷基异硫代氨基甲酸酯）；n = 0，x = 甲基 (Me)、乙基 (Et)、正丙基 (Pr) 和正丁基 (Bu)， A = PF 6 − , 1 Me [PF 6 ], 1 Et [PF 6 ] , 1 Pr [PF 6 ] , 1 Bu [PF 6 ] ; n = 1, x = Me, Et, Pr, and Bu, and A = PF 6 − , 2 Me [PF 6 ] , 2 Et [PF 6 ] , 2 Pr [PF 6 ] , and 2 Bu [PF 6 ] ; n
• Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments
  作者：Ying-Ying Huang、Yong He、Yang Liu、Jin-Hui Fu、Xiao-lin Liu、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1039/d3dt04226j

  日期：——

  To achieve fine regulation of FeII SCO behavior, a series of trinuclear cyanido-bridged complexes trans-[CpMen(dppe)MII(CN)]2[Fe1II(abpt)2](OTf)2 (1–4) (1, M = Fe2 and n = 1; 2, M = Fe2 and n = 4; 3, M = Fe2 and n = 5; 4, M = Ru and n = 5; CpMen = alkyl cyclopentadienyl with n = 1, 4, 5; dppe = 1,2-bis-(diphenylphosphino)ethane; abpt = 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and OTf = CF3SO3−)

  为了实现 Fe II SCO 行为的精细调控，一系列三核氰基桥配合物trans -[CpMe n (dppe)M II (CN)] 2 [Fe1 II (abpt) 2 ](OTf) 2 ( 1–4 ) ( 1 , M = Fe2 且n = 1; 2 , M = Fe2 且n = 4; 3 , M = Fe2 且n = 5; 4 , M = Ru 且n = 5; CpMe n = 烷基环戊二烯基，其中n = 1 , 4, 5; dppe = 1,2-双-(二苯基膦)乙烷；abpt = 4-氨基-3,5-双-(吡啶-2-基)-1,2,4-三唑且 OTf = CF 3 SO 3 - ) 通过元素分析、X 射线晶体学、磁性测量、变温红外光谱和穆斯堡尔光谱进行合成和充分表征。 值得一提的是，与许多单核Fe(abpt) 2 X 2 (X = NCS, NCSe, N(CN) 2 , C(CN) 3