215. Preparation and structural characterization of [CpRu(1,10-phenanthroline)(CH₃CN)][X] and precursor complexes (X= PF₆, BAr_F, TRISPHAT-N)
     Thierry Achard, Léo Egger, Cecillia Tortoreto, Laure Guénée, Jérôme Lacour
     Helv. Chim. Acta 2020, 103, e2000190

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 series of original transformations in 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 N-TRISPHAT⁻ 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)(CH3 CN)] [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.

DOI : 10.1002/hlca.202000190 

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