Treatment of Ru(H)Cl(CO)(PPh₃)₃ and Ru(H)Cl(CO)(PCy₃)₂ (Cy = cyclohexyl) with NaL_OEt (L_OEt^- = [(η⁵-C₅H₅)Co{P(O)(OEt)₂}₃]^-) afforded L_OEt(CO)(PR₃)RuH (R = Ph (1) and Cy (2)), which have been characterized by X-ray crystallography. It was found that the use of recrystallized samples of the Ru hydridesas starting materials and removal of the phosphines from the crude products with hexane are critical for the synthesis of complexes 1 and 2 in pure form. The protonation of 1 with HBF₄ in CD₂Cl₂ at low temperature resulted in appearance of new ¹H NMR signals at δ 11.78, -12.52 and -17.61 ppm, which can be assigned to Ru hydride species. The protonation of 1 with HCl in Et₂O afforded L_OEt(CO)(PR₃)RuCl. The reactions between 1 and RSO₂N₃ yielded the (arylsulfonyl)amido complexes L_OEt(CO)(PPh₃)R...[ Read more ]

Treatment of Ru(H)Cl(CO)(PPh₃)₃ and Ru(H)Cl(CO)(PCy₃)₂ (Cy = cyclohexyl) with NaL_OEt (L_OEt^- = [(η⁵-C₅H₅)Co{P(O)(OEt)₂}₃]^-) afforded L_OEt(CO)(PR₃)RuH (R = Ph (1) and Cy (2)), which have been characterized by X-ray crystallography. It was found that the use of recrystallized samples of the Ru hydridesas starting materials and removal of the phosphines from the crude products with hexane are critical for the synthesis of complexes 1 and 2 in pure form. The protonation of 1 with HBF₄ in CD₂Cl₂ at low temperature resulted in appearance of new ¹H NMR signals at δ 11.78, -12.52 and -17.61 ppm, which can be assigned to Ru hydride species. The protonation of 1 with HCl in Et₂O afforded L_OEt(CO)(PR₃)RuCl. The reactions between 1 and RSO₂N₃ yielded the (arylsulfonyl)amido complexes L_OEt(CO)(PPh₃)Ru(NHSO₂R) (R = 2,4,6-i-Pr₃C₆H₃ (3), 4-t-BuC₆H₄ (4), 4-MeC₆H₄ (5)). The crystal structure of 3 has been determined. The photolysis of 5 resulted in the complex L_OEt(MeCN)(PPh₃)Ru(NHSO₂C₆H₄Me-4). Treatment of Ru(PCy₃)₂(Cl)₂(=CHPh) with NaL_OEt afforded L_OEtRu(PCy₃)(Cl)(=CHPh) which can catalyze the ring-closing metathesis of diethyl 1,2-diallylmalonate. The reaction between (Et₄N)₂MoS₄ and NaL_OEt yielded the dinuclear Mo(V) sulfido complex [L_OEtMo(O)(μ-S)]₂ characterized by X-ray crystallography.

Four functionalized N^C ligands, 3-(pyridin-2-yl)phenol (HL1), diethyl hydroxy(4-(pyridin-2-yl)phenyl)ethylphosphonate (HL2), 2-(thiophen-3-yl)pyridine (HL3), and hydroxy(4-(pyridin-2-yl)phenyl)methylphosphonic acid (HL4), have been synthesized. Refluxing IrCl₃ with HL1 in methoxyethanol/H₂O gives [Ir(L1)₂Cl]₂. Treatment of [Ir(L1)₂Cl]₂ with 3 equivalents of silver triflate (AgOTf) yielded [Ir(L1)₂(dtbpy){Ag(MeCN)₂}](OTf)₂. The crystal structure of [Ir(L1)₂(dtbpy){Ag(MeCN)₂}](OTf)₂ shows that there is an interaction between the [Ag(MeCN)₂]⁺ moiety and the ipso carbons of the two L1 ligands. Reaction of [Ir(η⁵-C₅Me₅)Cl₂]₂ with HL2 in the presence of NaOAc resulted in the formation of Ir(η⁵-C₅Me₅)(L2)Cl. Reaction between LiL3 and [Ir(COD)Cl]₂ yielded [Ir(COD)(L3)] (COD = 1,4-cyclooctadiene) that underwent oxidative addition with MeI to give [Ir(COD)(L3)(CH₃)(I)]. The reaction between [Ru(η⁶-p-cymene)Cl₂]₂ and HL2 in the presence of NaOAc yielded Ru(η⁶-p-cymene)(L2)(Cl).