4-Coordinated, 14-electron ruthenium(ii) chalcogenolate complexes: synthesis, electronic structure and reactions with PhICl2 and organic azides

Abstract

The 4-coordinated Ru^II chalcogenolate complexes [Ru(STipp)₂(PPh₃)₂] (Tipp = 2,4,6-triisopropylphenyl, 1) and [Ru(SeMes)₂(PPh₃)₂] (Mes = 2,4,6-trimethylphenyl, 2) have been synthesized, and their reactions with PhICl₂ and organic azides have been studied. Complex 2 synthesized from [Ru^II(PPh₃)₃Cl₂] and NaSeMes displays a seesaw structure with P–Ru–P and Se–Ru–Se bond angles of 103.43(13) and 145.26(6)°, respectively. Natural bond order analyses revealed that in each of 1 and 2, there are two n → σ* (donor–acceptor) π interactions between the chalcogen lone pairs and the Ru–P antibonding molecular orbitals. The calculated second-order perturbation interaction energies of the two interactions for 1 (20.5 and 18.3 kcal mol⁻¹) are stronger than those of 2 (13.6 and 11.0 kcal mol⁻¹), suggesting the thiolate ligand (TippS⁻) is a stronger π-donor than the selenolate ligand (MesSe⁻) with respect to Ru^II. Chlorination of 1 with PhICl₂ afforded the dichloride complex [Ru(STipp)₂Cl₂(PPh₃)] (3), which was hydrolyzed to the hydroxo complex [Ru(STipp)₂(OH)Cl(PPh₃)] (4) after column chromatography on silica in air. Treatment of 4 with HCl and methyl triflate gave 3 and [Ru(STipp)₂(OH)(OTf)(PPh₃)] (OTf = triflate, 5), respectively. Reactions of 1 and 2 with p-tolyl azide (p-tolN₃) afforded the tetrazene complexes [Ru{N₄(p-tol)₂}(ER)₂(PPh₃)] (ER = STipp (6), SeMes (7)), whereas that with tosyl azide (TsN₃) gave the imido complexes [Ru(κ²-NTs)(STipp)₂(PPh₃)] (ER = STipp (8), SeMes (10)). The short Ru–N_imido distances in 8 [1.883(3) Å] and 10 [1.892(2) Å] are indicative of multiple bond character. Treatment of 8 with TsN₃ afforded the tetrazene complex [Ru(N₄Ts₂)(STipp)₂(PPh₃)] (9), but no cycloaddition was found between 10 and TsN₃. Nucleophilic attack of the imido ligand in 10 with methyl triflate yielded the amido complex [Ru(κ²-NMeTs)(SeMes)₂(PPh₃)](OTf) (11). The crystal structures of 2, 4, 6, and 8–11 have been determined.