Ru(IV) thiolate complexes [Ru(Sxylyl)
4(MeCN)] (Sxylyl = 2,6-dimethylphenyl), [Et
4N][Ru(Sxylyl)
4Cl] and [Et
4N] [Ru(Sxylyl)
3Cl
2] have been synthesized from [Et
4N] [RuCl
4(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 [ NH
4]
2[ OsCl
6] with Na(Sxylyl) in MeCN/MeOH afforded[Os(Sxylyl)
4(MeCN)] and [Os(Sxylyl)
3(MeCN)Cl]. Reaction of trans-OsO
2Cl
2(t-Bu
2bipy)] with C
6F
5SH gave [Os(SC
6F
5)
3(t-Bu
2bipy)Cl], which was characterized by X-ray crystallography. The first σ-acetylide complexes of Ru(IV) an...[
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Ru(IV) thiolate complexes [Ru(Sxylyl)
4(MeCN)] (Sxylyl = 2,6-dimethylphenyl), [Et
4N][Ru(Sxylyl)
4Cl] and [Et
4N] [Ru(Sxylyl)
3Cl
2] have been synthesized from [Et
4N] [RuCl
4(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 [ NH
4]
2[ OsCl
6] with Na(Sxylyl) in MeCN/MeOH afforded[Os(Sxylyl)
4(MeCN)] and [Os(Sxylyl)
3(MeCN)Cl]. Reaction of trans-OsO
2Cl
2(t-Bu
2bipy)] with C
6F
5SH gave [Os(SC
6F
5)
3(t-Bu
2bipy)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/Et
3N 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 (L
1), N,N'-bis(2-methylsulfinylbenzylidene)-diaminoethane (L
2) and (p-tolylsulfinyl)phenyl {(R)-(+)-[2-(3,3-dimethyl-2-oxazoline)]} (L
4) were synthesized. Treatment of [Ru(PPh
3)
3Cl
2] with ligands L
1 and L
2gave trans-[Ru(L
1)Cl
2] and trans-[Ru(L
2)Cl
2], respectively. Water-soluble trans-[Ru(L
2)(OH
2)Cl] [PF
6] has been synthesized from trans-[Ru(L
1)Cl
2] and Ag(I) and was found to catalyze cyclopropanation of styrene in water. trans-[Ru(L
2)C1
2] and trans-[Ru(L
2)(H
2O)Cl] [PF
6] have been characterized by X-ray diffraction. Reaction of [OsCl
2(PPh
3)
3] with L
2 afforded [Os(L
3(PPh
3)Cl
2)] (L
3 = N-(2-methylsulfinylbenzylidene)-N'-(2-methylsulfinylbenzylidene)-(R,R)-diaminocyclohexane), in which one of the sulfoxide groups has been deoxygenated by PPh
3. The palladium complex with bidentate imine-sulfoxide ligand [Pd(L
4)Cl
2] has been synthesized from [PdCl
2(MeCN)
2] and L
4[Ru{N(PPh
2Se)
2} {PPh
2(Se)NPPh
2}(NO)Cl] has been synthesized by reaction of [Ru(NO)Cl
3(PPh
3)
2] with K[N(PPh
2Se)
2]. trans-[OsO
2{Ph
2PN(Se)PPh
2}
2] was synthesized from trans-[K
2{OsO
2(OH)
4}] and Ph
2PNH(Se)PPh
2. Rhodium and iridium complexes with [N(PPh
3S)
2]
- have been synthesized. Treatment of [M(COD)C1]
2 (COD = 1,5-cyclooxtadiene) with K[N(PPh
3S)
2] afforded [M(COD){N(PPh
2S)
2}
2] (M = Ir, Rh). Reaction of [M(CO)(PPh
3)
2Cl] with K[N(PPh
3S)
2] gave [M(CO)(PPh
3){ N(PPh
2S)
2}
2] (M = Ir, Rh). The solid-state structure of [M(COD){N(PPh
2S)
2}
2] and [Ir(CO)(PPh
3){N(PPh
2S)
2}] have been determined by X-ray crystallography. Oxidative addition of [Ir(CO)(PPh
3){N(PPh
2S)
2}] with HCl and MeI gave Ir(III) complexes [Ir(CO)(PPh
3){N(PPh
2S)
2}(H)Cl] and [Ir(CO)(PPh
3){N(PPh
2S)
2}(Me)I], respectively.
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