[(PtCl)(Ru(C5Me5))(η6:κ3C,N,N'-2,6-bis(dimethylaminomethyl)phenyl)]BF4 | 1006388-71-1

• 英文名称: [(PtCl)(Ru(C5Me5))(η6:κ3C,N,N'-2,6-bis(dimethylaminomethyl)phenyl)]BF4
• CAS: 1006388-71-1
• 化学式: BF₄*C₂₂H₃₄ClN₂PtRu
• 分子量: 744.933
• InChiKey: LUECUOURSWLWBR-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：

  二氯甲烷 、 [(PtCl)(Ru(C5Me5))(η6:κ3C,N,N'-2,6-bis(dimethylaminomethyl)phenyl)]BF4 以 二氯甲烷 、 正戊烷 为溶剂， 生成 dichloromethane;1-[3-[(dimethylamino)methyl]benzene-2-id-1-yl]-N,N-dimethylmethanamine;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;platinum(2+);ruthenium(2+);chloride;tetrafluoroborate
  参考文献：
  名称：

  η⁶-Coordination of a Ruthenium(II) Organometallic Fragment to the Arene Ring of N,C,N-Pincer Metal Complexes

  摘要：

  Stable heterobimetallic complexes of the type [MX(NCN)Ru(C5R5)](+) (R = H or Me), where the phenylene ring of an NCN-pincer ligand coordinates first to a-platinum or palladium center via a a-bond, and second to a ruthenium organometallic fragment via a g-bond, are synthesized in a single step involving electrophilic attack of a cationic Ru species on the aryl metal complex. X-ray crystal structures and solution NMR agree on the simultaneous presence of orthogonal eta(6) - and eta(1)-coordination axes. Pt-195 NMR and electrochemistry show that the eta(6)-coordinated ruthenium fragment has a strong electron-withdrawing effect on the pincer metal, which leads to a diminished nucleophilicity of the platinum center toward electrophiles such as SO2.

  DOI：

  10.1021/om7009649
• 作为产物：
  描述：

  chloroplatinum(1+),1-[3-[(dimethylamino)methyl]benzene-2-id-1-yl]-N,N-dimethylmethanamine 、 [tris(acetonitrile)(η⁵-1,2,3,4,5-pentamethylcyclopentadienyl)ruthenium(II)][tetrafluoroborate] 以 二氯甲烷 为溶剂， 以96%的产率得到[(PtCl)(Ru(C5Me5))(η6:κ3C,N,N'-2,6-bis(dimethylaminomethyl)phenyl)]BF4
  参考文献：
  名称：

  η⁶-Coordination of a Ruthenium(II) Organometallic Fragment to the Arene Ring of N,C,N-Pincer Metal Complexes

  摘要：

  Stable heterobimetallic complexes of the type [MX(NCN)Ru(C5R5)](+) (R = H or Me), where the phenylene ring of an NCN-pincer ligand coordinates first to a-platinum or palladium center via a a-bond, and second to a ruthenium organometallic fragment via a g-bond, are synthesized in a single step involving electrophilic attack of a cationic Ru species on the aryl metal complex. X-ray crystal structures and solution NMR agree on the simultaneous presence of orthogonal eta(6) - and eta(1)-coordination axes. Pt-195 NMR and electrochemistry show that the eta(6)-coordinated ruthenium fragment has a strong electron-withdrawing effect on the pincer metal, which leads to a diminished nucleophilicity of the platinum center toward electrophiles such as SO2.

  DOI：

  10.1021/om7009649

文献信息

• SO2-binding properties of cationic η6,η1-NCN-pincer arene ruthenium platinum complexes: spectroscopic and theoretical studies
  作者：Sylvestre Bonnet、Joop H. van Lenthe、Hubertus J. J. van Dam、Gerard van Koten、Robertus J. M. Klein Gebbink

  DOI：10.1039/c0dt01437k

  日期：——

  The SO2-binding properties of a series of η6,η1-NCN-pincer ruthenium platinum complexes (NCN = 2,6-bis[(dimethylamino)methyl]phenyl anion) have been studied by both UV-visible spectroscopy and theoretical calculations. When an electron-withdrawing [Ru(C5R5)]+ fragment (R = H or Me) is η6-coordinated to the phenyl ring of the NCN-pincer platinum fragment (cf. [2]+ and [3]+, see Scheme 1), the characteristic orange coloration (pointing to η1- SO2 binding to Pt) of a solution of the parent NCN-pincer platinum complex 1 in dichloromethane upon SO2-bubbling is not observed. However, when the ruthenium center is η6-coordinated to a phenyl substituent linked in para-position to the carbon-to-platinum bond, i.e. complex [4]+, the SO2-binding property of the NCN-platinum center seems to be retained, as bubbling SO2 into a solution of the latter complex produces the characteristic orange color. We performed theoretical calculations at the MP2 level of approximation and TD-DFT studies, which enabled us to interpret the absence of color change in the case of [2]+ as an absence of coordination of SO2 to platinum. We analyze this absence or weaker SO2-coordination in dichloromethane to be a consequence of the relative electron-poorness of the platinum center in the respective η6-ruthenium coordinated NCN-pincer platinum complexes, that leads to a lower binding energy and an elongated calculated Pt–S bond distance. We also discuss the effects of electrostatic interactions in these cationic systems, which also seems to play a destabilizing role for complex [2(SO2)]+.

  一系列的η6,η1-NCN-夹心铑-铂配合物的SO2结合特性通过紫外-可见光谱和理论计算进行了研究（NCN = 2,6-双[(二甲基氨基)甲基]苯基阴离子）。当一个吸电子的[Ru(C5R5)]+片段（R = H 或 Me）以η6方式与NCN-夹心铂片段的苯环配位时（参见[2]+和[3]+，见方案1），在二氯甲烷中SO2通入时，母体NCN-夹心铂配合物1的溶液没有观察到特征性的橙色（表明η1-SO2与铂的结合）。然而，当铑中心以η6方式与位于碳-铂键旁位的苯取代基配位时，即复合物[4]+，NCN-铂中心的SO2结合特性似乎得以保留，因为在后者复合物的溶液中通入SO2会产生特征性的橙色。我们在MP2近似水平和TD-DFT研究上进行了理论计算，这使我们能够解释[2]+中颜色变化缺失的原因，即SO2未与铂配位。我们分析这种在二氯甲烷中缺失或弱SO2配位的现象为相应的η6-铑配位NCN-夹心铂配合物中铂中心的相对缺电子性，导致结合能降低和计算得到的Pt–S键距离延长。我们还讨论了这些阳离子体系中静电相互作用的影响，这似乎也对复合物[2(SO2)]+起到了不稳定的作用。