[trans-Cl(η2-dppe)2Ru(CO)](1+) | 92940-68-6

• 英文名称: [trans-Cl(η2-dppe)2Ru(CO)](1+)
• CAS: 92940-68-6
• 化学式: C₅₃H₄₈ClOP₄Ru
• 分子量: 961.382
• InChiKey: OBQRJGWAFXLJJB-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  [trans-Cl(η2-dppe)2Ru(CCC6H4-p-NO2)][BF4] 在 NOPF₆ 作用下， 以 not given 为溶剂， 生成 [trans-Cl(η2-dppe)2Ru(CO)](1+)
  参考文献：
  名称：

  Bonding and Electron Delocalization in Ruthenium(III) σ-Arylacetylide Radicals [trans-Cl(η²-dppe)₂RuC≡C(4-C₆H₄X)]⁺ (X = NO₂, C(O)H, C(O)Me, F, H, OMe, NMe₂): Misleading Aspects of the ESR Anisotropy

  摘要：

  The bonding within the series of [trans-Cl(eta(2)-dppe)(2)RuC C(4-C6H4X)](n+) complexes (1-Xn+; n = 1, 0 and X = NO2, C(O)H, C(O)Me, F, H, OMe, NMe2) has been examined by IR, ESR, and UV-vis-near-IR spectroscopy together with computational modelin. A strong substituent effect is evidenced for radical delocalization from the metal to the functional arylacetylide fragment. This effect is also apparent in the large anisotropy change of their ESR signatures. DFT calculations substantiate these experimental observations and permit discussion of the influence of the X substituent on spin delocalization in compounds containing. isolobal metal fragments. Evidence is given that the ESR anisotropy alone cannot reliably be used to compare the metallic character of the unpaired electrons in closely related families of pseudooctahedral cationic Ru(III) functional arylacetylides with rhombic symmetry when the complexes possess different coordination spheres. ESR anisotropy constitutes nevertheless a useful benchmark for this purpose within the presently investigated 1-X+ family.

  DOI：

  10.1021/om801138q

文献信息

• Silver(I)-mediated isomerisation of trans-[RuCl2(P–P)2] (P–P = four-membered ring chelate diphosphine ligand) to cis-[{Ru(P–P)2(μ-Cl)2}nAg]+ species, and applications in stereoselective syntheses of cis- and trans-[RuCl(L)(P–P)2]+ (L = neutral ligand) †
  作者：Simon J. Higgins、Annemarie La Pensée、Clare A. Stuart、John M. Charnock

  DOI：10.1039/b009645h

  日期：——

  mixture, which includes cis-[RuCl2(diphos)2], and species of the type [Ru(diphos)2(μ-Cl)2}nAg]+ (n = 1 or 2) in which the exact coordination geometry at AgI is unknown. The reactions have been followed by 31P-1H} NMR spectroscopy, and electronic spectroscopy results also support the isomerisation. The ruthenium and silver K-edge EXAFS spectra of the solid isolated from the reaction of trans-[RuCl2(dppm)2]

  当络合物反式-[RuCl 2（diphos）2 ]（敌敌畏 =（Ph 2 P）2 C CH 2，Ph 2 PCH 2 PPh 2或Ph 2 PNHPPh 2）银盐在1,2-二氯乙烷卤化物中，配位差的阴离子（例如AgBF 4，AgO 3 SCF 3）的吸收缓慢，即使在回流下，反应也通过有趣的机理进行，该机理涉及反式至顺式异构化。在室温下，会形成特征为[RuCl（diphos）2（μ-Cl）Ag] +的络合物。加热至回流5-10分钟后，其反应生成包括顺式-[RuCl 2（diphos）2 ]和类型为Ru（diphos）2（μ-Cl）2 } n Ag的物质的混合物。] +（n  = 1或2），其中Ag I的确切配位几何形状未知。反应之后是31 P- 1 H}核磁共振波谱， 和 电子光谱学结果也支持异构化。钌和银K边缘EXAFS 光谱从反式-[RuCl 2（dppm）2 ]和AgO 3 SCF