Please use this identifier to cite or link to this item: http://hdl.handle.net/1783.1/4017

Ruthenium complexes with thiolate and sulfoxide ligands

Authors Lai, Chui Ying
Issue Date 2002
Summary 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.
Note Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2002
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