Preparation and Structural Characterization of [CpRu(1,10‐phenanthroline)(CH3CN)][X] and Precursor Complexes (X=PF6, BArF, TRISPHAT‐N),Helvetica Chimica Acta

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Preparation and Structural Characterization of [CpRu(1,10‐phenanthroline)(CH3CN)][X] and Precursor Complexes (X=PF6, BArF, TRISPHAT‐N)
Helvetica Chimica Acta ( IF 1.5 ) Pub Date : 2020-10-23 , DOI: 10.1002/hlca.202000190
Thierry Achard ₁ , Léo Egger ₁ , Cecilia Tortoreto ₁ , Laure Guénée ₂ , Jérôme Lacour ₁

Affiliation

Cationic [Ru(η⁵‐C₅H₅)(CH₃CN)₃]⁺ complex, tris(acetonitrile)(cyclopentadienyl)ruthenium(II), gives rise to a very rich organometallic chemistry. Combined with diimine ligands, and 1,10‐phenanthroline in particular, this system efficiently catalyzes diazo decomposition processes to generate metal‐carbenes which undergo a series of original transformations in the presence of Lewis basic substrates. Herein, syntheses and characterizations of [CpRu(Phen)(L)] complexes with (large) lipophilic non‐coordinating (PF₆⁻ and BAr_F⁻) and coordinating TRISPHAT‐N⁻ anions are reported. Complex [CpRu(η⁶‐naphthalene)][BAr_F] ([1][BAr_F]) is readily accessible, in high yield, by direct counterion exchange between [1][PF₆] and sodium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (NaBAr_F) salts. Ligand exchange of [1][BAr_F] in acetonitrile generated stable [Ru(η⁵‐C₅H₅)(CH₃CN)₃][BAr_F] ([2][BAr_F]) complex in high yield. Then, the desired [CpRu(Phen)(CH₃CN)] ([3]) complexes were obtained from either the [1] or [2] complex in the presence of the 1,10‐phenanthroline as ligand. For characterization and comparison purposes, the anionic hemilabile ligand TRISPHAT−N (TTN) was introduced on the ruthenium center, from the complex [3][PF₆], to quantitatively generate the desired complex [CpRu(Phen)(TTN)] ([4]) by displacement of the remaining acetonitrile ligand and of the PF₆⁻ anion. Solid state structures of complexes [1][BAr_F], [2][BAr_F], [3][BAr_F], [3][PF₆] and [4] were determined by X‐ray diffraction studies and are discussed herein.

中文翻译：

[CpRu（1,10-菲咯啉）（CH3CN）] [X]和前体配合物（X = PF6，BArF，TRISPHAT‐N）的制备和结构表征

阳离子的[Ru（η ⁵ -C ₅ H ^ ₅）（CH ₃ CN）₃ ] ⁺络合物，三（乙腈）（环戊二烯基）钌（II），产生了非常丰富的有机金属化学。该系统与二亚胺配体（尤其是1,10-菲咯啉）结合使用，可有效催化重氮分解过程，生成金属卡宾，在路易斯碱性底物存在下，卡宾会经历一系列原始转化。本文中，[CPRU（phen）的（L）]的合成和表征与（大）的亲脂性非配位复合物（PF ₆^-和酒吧_˚F^-）和协调TRISPHAT-N ^-据报道有阴离子。络合物[CPRU（η ⁶ -萘）] [BAR _˚F ]（[1] [巴_˚F ]）是容易访问的，以高收率，通过之间的直接交换抗衡离子[1] [PF ₆ ]和钠四[3,5- -双（三氟甲基）苯基]硼酸盐（NaBAr _F）盐。配体的交换[1] [巴_˚F ]在乙腈中产生稳定的[Ru（η ⁵ -C ₅ H ^ ₅）（CH ₃ CN）₃ ] [巴_˚F ]（[2] [巴_˚F ]）以高收率复杂。然后，所需的[CpRu（Phen）（CH ₃CN）]（[3]）络合物是在[1]或[2]络合物中以1,10-菲咯啉作为配体存在的。为了进行表征和比较，将阴离子半不稳定的配体TRISPHAT-N（TTN）从配合物[3] [PF ₆ ]引入钌中心，以定量生成所需的配合物[CpRu（Phen）（TTN）]（[4]由剩余的乙腈配体和PF的位移）₆^-的阴离子。配合物[1] [BAr _F ]，[2] [BAr _F ]，[3] [BAr _F ]的固态结构，[3] [PF ₆ ]和[4]是通过X射线衍射研究确定的，并在本文中进行了讨论。

更新日期：2020-12-11

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