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Chemical Control on the Coordination Mode of Benzaldehyde Semicarbazone Ligands. Synthesis, Structure, and Redox Properties of Ruthenium Complexes

Reaction of benzaldehyde semicarbazone (HL-R, where H is a dissociable proton and R is a substituent (R = OMe, Me, H, Cl, NO2) at the para position of the phenyl ring) with [Ru(PPh3)3Cl2] and [Ru(PPh3)2(CO)2Cl2] has afforded complexes of different types. When HL-NO2 and [Ru(PPh3)3Cl2] react in solution at ambient temperature, trans-[Ru(PPh3)2(L-NO2)Cl] is obtained. Its structure determination by X-ray crystallography shows that L-NO2 is coordinated as a tridentate C,N,O-donor ligand. When reaction between HL-NO2 and [Ru(PPh3)3Cl2] is carried out in refluxing ethanol, a more stable cis isomer of [Ru(PPh3)2(L-NO2)Cl] is obtained. The trans isomer can be converted to the cis isomer simply by providing appropriate thermal energy. Slow reaction of HL-R with [Ru(PPh3)2(CO)2Cl2] in solution at ambient temperature yields 5-[Ru(PPh3)2(L-R)(CO)Cl] complexes. A structure determination of 5-[Ru(PPh3)2(L-NO2)(CO)Cl] shows that the semicarbazone ligand is coordinated as a bidentate N,O-donor, forming a five-membered chelate ring. When reaction between HL-R and [Ru(PPh3)2(CO)2Cl2] is carried out in refluxing ethanol, the 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes are obtained. A structure determination of 4-[Ru(PPh3)2(L-NO2)(CO)Cl] shows that a semicarbazone ligand is bound to ruthenium as a bidentate N,O-donor, forming a four-membered chelate ring. All the complexes are diamagnetic (low-spin d6, S = 0). The trans- and cis-[Ru(PPh3)2(L-NO2)Cl] complexes undergo chemical transformation in solution. The 5- and 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes show sharp NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry of the 5-[Ru(PPh3)2(L-R)(CO)Cl] and 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes show the Ru(II)−Ru(III) oxidation to be within 0.66−1.07 V. This oxidation potential is found to linearly correlate with the Hammett constant of the substituent R

Unusual Coordination Mode of Thiosemicarbazone Ligands. A Search for the Origin

Twelve mixed-ligand thiosemicarbazone complexes of ruthenium and osmium, ten of general formula [M(bpy)2(bztsc−R)]ClO4, (M = Ru, Os; bpy = 2,2‘-bipyridine, Hbztsc−R = benzaldehyde thiosemicacbazone) and two of type [M(bpy)2(actsc)]ClO4 (Hactsc = acetonethiosemicarbazone), have been synthesized and characterized. All the complexes are diamagnetic (low-spin d6, S = 0) and in acetonitrile solution show several intense metal-to-ligand charge-transfer (MLCT) transitions in the visible region. Structures of Hbztsc−OMe, [Ru(bpy)2(bztsc−NO2)]ClO4 and [Ru(bpy)2(actsc)]ClO4 have been determined by X-ray crystallography. Benzaldehyde thiosemicarbazone exists in the thione form with the phenyl group trans to the hydrazinic nitrogen. The benzaldehyde thiosemicarbazone ligand coordinates to the metals through the hydrazinic nitrogen and sulfur with a bite angle of ∼67°, forming a four-membered chelate ring. However, the actsc ligand coordinates through the imine nitrogen and sulfur, forming a five-membered chelate ring with a bite angle of ∼81°. The difference in coordination modes of two types of thiosemicarbazone ligands, viz., bztsc−R and actsc, appears to result from the difference in steric bulk of the aryl and methyl group trans to the hydrazinic nitrogen. In acetronitrile solution they all show a reversible metal(II)−metal(III) oxidation in the range 0.18−0.58 V vs SCE followed by an irreversible oxidation in the range 1.11−1.60 V vs SCE. Two successive one-electron reductions of the coordinated bipyridine are also observed in the range −1.53 to −1.96 V vs SCE

Ligand Control on Molecular Oxygen Activation by Rhodium Quinone Complexes

Ligand Control on Molecular Oxygen Activation by Rhodium Quinone Complexe

Steric Control of the Coordination Mode of the Salicylaldehyde Thiosemicarbazone Ligand. Syntheses, Structures, and Redox Properties of Ruthenium and Osmium Complexes

Steric Control of the Coordination Mode of the Salicylaldehyde Thiosemicarbazone Ligand. Syntheses, Structures, and Redox Properties of Ruthenium and Osmium Complexe

Chemical Control on the Coordination Mode of Benzaldehyde Semicarbazone Ligands. Synthesis, Structure, and Redox Properties of Ruthenium Complexes

Reaction of benzaldehyde semicarbazone (HL-R, where H is a dissociable proton and R is a substituent (R = OMe, Me, H, Cl, NO2) at the para position of the phenyl ring) with [Ru(PPh3)3Cl2] and [Ru(PPh3)2(CO)2Cl2] has afforded complexes of different types. When HL-NO2 and [Ru(PPh3)3Cl2] react in solution at ambient temperature, trans-[Ru(PPh3)2(L-NO2)Cl] is obtained. Its structure determination by X-ray crystallography shows that L-NO2 is coordinated as a tridentate C,N,O-donor ligand. When reaction between HL-NO2 and [Ru(PPh3)3Cl2] is carried out in refluxing ethanol, a more stable cis isomer of [Ru(PPh3)2(L-NO2)Cl] is obtained. The trans isomer can be converted to the cis isomer simply by providing appropriate thermal energy. Slow reaction of HL-R with [Ru(PPh3)2(CO)2Cl2] in solution at ambient temperature yields 5-[Ru(PPh3)2(L-R)(CO)Cl] complexes. A structure determination of 5-[Ru(PPh3)2(L-NO2)(CO)Cl] shows that the semicarbazone ligand is coordinated as a bidentate N,O-donor, forming a five-membered chelate ring. When reaction between HL-R and [Ru(PPh3)2(CO)2Cl2] is carried out in refluxing ethanol, the 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes are obtained. A structure determination of 4-[Ru(PPh3)2(L-NO2)(CO)Cl] shows that a semicarbazone ligand is bound to ruthenium as a bidentate N,O-donor, forming a four-membered chelate ring. All the complexes are diamagnetic (low-spin d6, S = 0). The trans- and cis-[Ru(PPh3)2(L-NO2)Cl] complexes undergo chemical transformation in solution. The 5- and 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes show sharp NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry of the 5-[Ru(PPh3)2(L-R)(CO)Cl] and 4-[Ru(PPh3)2(L-R)(CO)Cl] complexes show the Ru(II)−Ru(III) oxidation to be within 0.66−1.07 V. This oxidation potential is found to linearly correlate with the Hammett constant of the substituent R

Bis(amido)ruthenium(IV) Complexes with 2,3-Diamino-2,3-dimethylbutane. Crystal Structure and Reversible Ru(IV)−Amide/Ru(III)−Amine and Ru(IV)−Amide/Ru(II)− Amine Redox Couples in Aqueous Solution

Two bis(amido)ruthenium(IV) complexes, [RuIV(bpy)(L-H)2]2+ and [RuIV(L)(L-H)2]2+ (bpy = 2,2‘-bipyridine, L = 2,3-diamino-2,3-dimethylbutane, L-H = (H2NCMe2CMe2NH)-), were prepared by chemical oxidation of [RuII(bpy)(L)2]2+ and the reaction of [(n-Bu)4N][RuVINCl4] with L, respectively. The structures of [Ru(bpy)(L-H)2][ZnBr4]·CH3CN and [Ru(L)(L-H)2]Cl2·2H2O were determined by X-ray crystal analysis. [Ru(bpy)(L-H)2][ZnBr4]·CH3CN crystallizes in the monoclinic space group P21/n with a = 12.597(2) Å, b = 15.909(2) Å, c = 16.785(2) Å, β = 91.74(1)°, and Z = 4. [Ru(L)(L-H)2]Cl2·2H2O crystallizes in the tetragonal space group I41/a with a = 31.892(6) Å, c = 10.819(3) Å, and Z = 16. In both complexes, the two Ru−N(amide) bonds are cis to each other with bond distances ranging from 1.835(7) to 1.856(7) Å. The N(amide)−Ru−N(amide) angles are about 110°. The two Ru(IV) complexes are diamagnetic, and the chemical shifts of the amide protons occur at around 13 ppm. Both complexes display reversible metal−amide/metal−amine redox couples in aqueous solution with a pyrolytic graphite electrode. Depending on the pH of the media, reversible/quasireversible 1e-−2H+ Ru(IV)−amide/Ru(III)−amine and 2e-−2H+ Ru(IV)−amide/Ru(II)−amine redox couples have been observed. At pH = 1.0, the E° is 0.46 V for [RuIV(bpy)(L-H)2]2+/[RuIII(bpy)(L)2]3+ and 0.29 V vs SCE for [RuIV(L)(L-H)2]2+/[RuIII(L)3]3+. The difference in the E° values for the two Ru(IV)−amide complexes has been attributed to the fact that the chelating saturated diamine ligand is a better σ-donor than 2,2‘-bipyridine

WCl(η²-C₂Ph₂)(η⁶-C₆Ph₆H): A Compound Containing a Metallacycloheptatriene Unit from Trimerization of Diphenylacetylene with W(NMe₃)(η²-C₂Ph₂)₃

W(NCMe)(η2-C2Ph2)3 (1) has been previously synthesized by the reaction of W(CO)(η2-C2Ph2)3 with Me3NO in acetonitrile, while the same treatment in THF leads to the trimethylamine complex W(NMe3)(η2-C2Ph2)3 (2). Compound 2 is reactive. Stirring a mixture of 2 and diphenylacetylene in dichloromethane at room temperature affords WCl(η2-C2Ph2)(η6-C6Ph6H) (3), which apparently arises from trimerization of the alkyne ligands concomitant with solvent activation. The structures of 1−3 have been determined by an X-ray diffraction study. A carbene WC double bond is evidenced in 3

Syntheses and Structures of Tungsten <i>o</i>-(Diphenylphosphino)benzaldehyde Complexes Bearing π-Bonded Aldehyde Groups

Reaction of the bidentate ligand Ph2P(o-C6H4)C(O)H (abbreviated as PCHO) with W(CO)3(η3-(MeNCH2)3) at room temperature affords W(CO)3(η1-PCHO)(η3-PCHO) (1), which subsequently loses a carbonyl ligand to give W(CO)2(η3-PCHO)2 (2). Further treatment of 2 with PCHO in refluxing benzene results in carbon−carbon coupling of the PCHO ligands to produce W(CO)(η3-PCHO)(η3-(PCHO)2) (3). The structures of 1−3 have been determined by an X-ray diffraction study. The PCHO ligands in these compounds act as chelating phosphine−aldehydes with the aldehyde groups coordinating in a π fashion

WCl(η²-C₂Ph₂)(η⁶-C₆Ph₆H): A Compound Containing a Metallacycloheptatriene Unit from Trimerization of Diphenylacetylene with W(NMe₃)(η²-C₂Ph₂)₃

W(NCMe)(η2-C2Ph2)3 (1) has been previously synthesized by the reaction of W(CO)(η2-C2Ph2)3 with Me3NO in acetonitrile, while the same treatment in THF leads to the trimethylamine complex W(NMe3)(η2-C2Ph2)3 (2). Compound 2 is reactive. Stirring a mixture of 2 and diphenylacetylene in dichloromethane at room temperature affords WCl(η2-C2Ph2)(η6-C6Ph6H) (3), which apparently arises from trimerization of the alkyne ligands concomitant with solvent activation. The structures of 1−3 have been determined by an X-ray diffraction study. A carbene WC double bond is evidenced in 3