Ru(IV) thiolate complexes [Ru(Sxylyl)₄(MeCN)] (Sxylyl = 2,6-dimethylphenyl), [Et₄N][Ru(Sxylyl)₄Cl] and [Et₄N] [Ru(Sxylyl)₃Cl₂] have been synthesized from [Et₄N] [RuCl₄(MeCN)₂] and Na(Sxylyl) in MeCN/MeOH and characterized by X-ray crystallography. Protonation of [Ru(Sxylyl)₄(MeCN)] with HCl afforded [Ru(Sxylyl)₃Cl(MeCN)]. The adducts [Ru(Sxylyl)₄(pyz)] (pyz = pyrazine) and [Ru(Sxylyl)]₂(μ-CNpy) (CNpy = 4-cyanopyridine) were synthesized by reacting [Ru(Sxylyl)₄(MeCN)] with pyz and 4-CNpy, respectively. Treatment of [ NH₄] ₂[ OsCl₆] with Na(Sxylyl) in MeCN/MeOH afforded[Os(Sxylyl)₄(MeCN)] and [Os(Sxylyl)₃(MeCN)Cl]. Reaction of trans-OsO₂Cl₂(t-Bu₂bipy)] with C₆F₅SH gave [Os(SC₆F₅)₃(t-Bu₂bipy)Cl], which was characterized by X-ray crystallography. The first σ-acetylide complexes of Ru(IV) an...[ Read more ]

Ru(IV) thiolate complexes [Ru(Sxylyl)₄(MeCN)] (Sxylyl = 2,6-dimethylphenyl), [Et₄N][Ru(Sxylyl)₄Cl] and [Et₄N] [Ru(Sxylyl)₃Cl₂] have been synthesized from [Et₄N] [RuCl₄(MeCN)₂] and Na(Sxylyl) in MeCN/MeOH and characterized by X-ray crystallography. Protonation of [Ru(Sxylyl)₄(MeCN)] with HCl afforded [Ru(Sxylyl)₃Cl(MeCN)]. The adducts [Ru(Sxylyl)₄(pyz)] (pyz = pyrazine) and [Ru(Sxylyl)]₂(μ-CNpy) (CNpy = 4-cyanopyridine) were synthesized by reacting [Ru(Sxylyl)₄(MeCN)] with pyz and 4-CNpy, respectively. Treatment of [ NH₄] ₂[ OsCl₆] with Na(Sxylyl) in MeCN/MeOH afforded[Os(Sxylyl)₄(MeCN)] and [Os(Sxylyl)₃(MeCN)Cl]. Reaction of trans-OsO₂Cl₂(t-Bu₂bipy)] with C₆F₅SH gave [Os(SC₆F₅)₃(t-Bu₂bipy)Cl], which was characterized by X-ray crystallography. The first σ-acetylide complexes of Ru(IV) and Os(IV) thiolates [M(Sxylyl)₃(CΞCPh)C1]^-have been synthesized from [M(Sxylyl)₃(MeCN)Cl] (M = Ru, Os) and PhCΞCH/Et₃N and characterized by X-ray crystallography. [Ru(Sxylyl)₃(CΞCPh)Cl]^- was reduced by t-BuNC to give trans-[Ru(t-BuNC)₄(Sxylyl)₂]. [Ru(Sxylyl)₃(CΞCPh)Cl]^- was found to catalyze cyclopropanation of styrene and ring-opening polymerization of norbornene.

New quadridentate and bidentate imine-sulfoxide ligands, N,N'-bis(2-methylsulfinylbenzylidene)-(R,R)-diaminocyclohexane (L¹), N,N'-bis(2-methylsulfinylbenzylidene)-diaminoethane (L²) and (p-tolylsulfinyl)phenyl {(R)-(+)-[2-(3,3-dimethyl-2-oxazoline)]} (L⁴) were synthesized. Treatment of [Ru(PPh₃)₃Cl₂] with ligands L¹ and L²gave trans-[Ru(L¹)Cl₂] and trans-[Ru(L²)Cl₂], respectively. Water-soluble trans-[Ru(L²)(OH₂)Cl] [PF₆] has been synthesized from trans-[Ru(L¹)Cl₂] and Ag(I) and was found to catalyze cyclopropanation of styrene in water. trans-[Ru(L²)C1²] and trans-[Ru(L²)(H₂O)Cl] [PF₆] have been characterized by X-ray diffraction. Reaction of [OsCl₂(PPh₃)₃] with L² afforded [Os(L³(PPh₃)Cl₂)] (L³ = N-(2-methylsulfinylbenzylidene)-N'-(2-methylsulfinylbenzylidene)-(R,R)-diaminocyclohexane), in which one of the sulfoxide groups has been deoxygenated by PPh₃. The palladium complex with bidentate imine-sulfoxide ligand [Pd(L⁴)Cl₂] has been synthesized from [PdCl₂(MeCN)₂] and L⁴

[Ru{N(PPh₂Se)₂} {PPh₂(Se)NPPh₂}(NO)Cl] has been synthesized by reaction of [Ru(NO)Cl₃(PPh₃)₂] with K[N(PPh₂Se)₂]. trans-[OsO₂{Ph₂PN(Se)PPh₂}₂] was synthesized from trans-[K₂{OsO₂(OH)₄}] and Ph₂PNH(Se)PPh₂. Rhodium and iridium complexes with [N(PPh₃S)₂]^- have been synthesized. Treatment of [M(COD)C1]₂ (COD = 1,5-cyclooxtadiene) with K[N(PPh₃S)₂] afforded [M(COD){N(PPh₂S)₂}₂] (M = Ir, Rh). Reaction of [M(CO)(PPh₃)₂Cl] with K[N(PPh₃S)₂] gave [M(CO)(PPh₃){ N(PPh₂S)₂}₂] (M = Ir, Rh). The solid-state structure of [M(COD){N(PPh₂S)₂}₂] and [Ir(CO)(PPh₃){N(PPh₂S)₂}] have been determined by X-ray crystallography. Oxidative addition of [Ir(CO)(PPh₃){N(PPh₂S)₂}] with HCl and MeI gave Ir(III) complexes [Ir(CO)(PPh₃){N(PPh₂S)₂}(H)Cl] and [Ir(CO)(PPh₃){N(PPh₂S)₂}(Me)I], respectively.