Linkage isomerism of pentaammine(dimethylsulfoxide)ruthenium(II/III) complexes: A theoretical study

Kato, Masaru; Takayanagi, Toshiyuki; Fujihara, Takashi; Nagasawa, Akira

doi:10.1016/j.ica.2008.06.012

Cited by 12 publications

(10 citation statements)

References 37 publications

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“…Similar computational results were reported on linkage isomers of [Ru(NH 3 ) 5 (DMSO)] n+ . 40 Our calculations suggest that the solvation effect may be important for the formation of 2 and 3.…”

Section: ■ Results and Discussionmentioning

confidence: 72%

“…MIO is an amide compound with a five-membered ring. N , N -Dimethylformamide (DMF) is also an amide compound, but its p K a is 1.20, , which is lower than that of MIOHCl. This difference in p K a between MIO and DMF may come from stabilization of the protonated form by delocalization of the positive charge over the planar five-membered ring because the p K a value of the 3-hydroxy moiety for 3-isothiazolole is similar (p K a = 7.54) .…”

Section: Results and Discussionmentioning

confidence: 99%

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Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Kato

Unoura²,

Takayanagi

et al. 2013

Inorg. Chem.

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Five metal complexes of 2-methylisothiazol-3(2H)-one (MIO), [Co(III)(NH3)5(MIO)](3+), [Ru(II)(NH3)5(MIO)](2+), [Ru(III)(NH3)5(MIO)](3+), [Pt(II)Cl3(MIO)](-), and trans-[U(VI)O2(NO3)2(MIO)2], were synthesized, and their structures were determined by single-crystal X-ray crystallography. MIO is an ambidentate ligand and coordinates to metal centers through its oxygen atom in the cobalt(III), ruthenium(III), and uranium(VI) complexes and through its sulfur atom in the ruthenium(II) and platinum(III) complexes. This result suggests that MIO shows preferential behavior on its donating atoms. We also studied the electron-donor abilities of the oxygen and sulfur atoms of MIO. Various physical measurements on the conjugate acid of MIO and the MIO complexes allowed us to determine an acid dissociation constant (pKa) and donor number (DN) for the oxygen atom of MIO and Lever's electrochemical parameter (EL) and a relative covalency parameter (kL) for the sulfur atom.

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Section: ■ Results and Discussionmentioning

confidence: 72%

Section: Results and Discussionmentioning

confidence: 99%

Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Kato

Unoura²,

Takayanagi

et al. 2013

Inorg. Chem.

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“…Much effort has been devoted to the investigation of the variable S O dimensions of dialkyl sulfoxides upon metal coordination and their related properties (Cotton & Francis, 1960;Alessio, 2004). The C-S(O)-C fragment with C s local symmetry endows the dialkyl sulfoxide with flexible coordination sites at the S and/or O atoms, exhibiting 1 -O-bonded, 1 -S-bonded and -S,O-bonded modes with diverse S O bond lengths (Calligaris, 2004;Kato et al, 2009). Grafting pyridine groups onto a selected organic fragment is a method generally used by supramolecular chemists to construct various coordination architectures with interesting properties.…”

Section: Commentmentioning

confidence: 99%

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]

Wan

Wang²,

Qiao³

et al. 2012

Acta Crystallogr C

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In the title complex, [Ag(NO(3))(C(9)H(7)N(3)OS)](n), η(1):η(1):η(1):μ(2)-bridging 2-(pyridin-4-ylsulfinyl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag(I) cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [ ̅201] direction. An FT-IR spectroscopic study shows a decreased stretching frequency for the η(1)-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and interconnected via O(S=O)···π(pyridine/pyrimidine) and C-H(pyridine)···O(NO(3)(-)) interactions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO(3)(-))···π(pyrimidine) interactions to form a three-dimensional supramolecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)···π(pyridine/pyrimidine) and anion(NO(3)(-))...π(pyrimidine) interactions in the supramolecular assembly of the title complex are presented.

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“…A purple solid was removed by filtration, redissolved in 60 mL of a methanol/NH 4 PF 6(aq., 3 M) mixture (20 : 1) and precipitated by addition of some H 2 O to the solution and then decreasing the volume to yield 167 mg of the product (0.227 mmol, 48%). Elemental analysis (%) calcd for C 29 H 22 .32 (t, 3 J 12-11 = 3 J 12-13 = 7.7 Hz, 1H; H12), 8.18 (t, 3 J 22-21 = 8 Hz, 1H; H22), 7.98 (t, 3 J 17-16 = 3 J 17-18 = 7.8 Hz, 2H; H17, H27), 7.9 (t, 3 J 1-12 = 3 J 13-14 = 6.6 Hz, 1H; H13), 7.71 (s, H8), 7.64 (d, 3 J 15-16 = 3 J 29-28 = 5.3 Hz, 2H; H15, H29), 7.45 (d, 3 J 1-2 = 3 J 5-4 = 6.9 Hz, 2H; H1, H5), 7.38 (m, 5H; H2, H3, H4, H16, H28). NOESY (400 MHz, DMSO-d 6 ): d = 7.71-7.45 (H8-H1 or H8-H5), 7.71-8.51 (H8-H11).…”

Section: X-ray Crystallographymentioning

confidence: 99%

The RuIVO-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies

et al. 2010

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Two Ru(IV)=O catalysts with either a pentadentate bispidine ligand L(1) or a bidentate pyrazolate L(2)/terpy L(3) combination of ligands have very different efficiencies as oxygen transfer catalysts for the selective oxidation of sulfides to sulfoxides: the [Ru(II)(L(1))(solvent)](2+)/iodosyl benzene system has an initial TOF of approx. 40 h(-1) and quantitative yield, with [Ru(II)(L(2))(L(3))(solvent)](+) the initial TOF is approx. 12 h(-1) with a maximum yield of approx. 60%. By experiment (cyclovoltametry) it is shown that there is S- to O-linkage isomerization of the Ru(II) sulfoxide product complex, and this may partially switch off the catalytic cycle for the L(2)/L(3)-based catalyst. It emerges that the reasons for the reduced efficiency in the case of the L(2)/L(3), in comparison with the L(1)-based catalyst, are a more efficient linkage isomerization, a more stable S-bonded, in comparison with the O-bonded, Ru(II)-based isomer, and inefficient ligand exchange in the product (hydrolysis produces the free sulfoxide and the Ru(II) precatalyst). These interpretations are qualitatively in good agreement with preliminary DFT-based data.

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Linkage isomerism of pentaammine(dimethylsulfoxide)ruthenium(II/III) complexes: A theoretical study

Cited by 12 publications

References 37 publications

Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]

The RuIVO-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies

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Linkage isomerism of pentaammine(dimethylsulfoxide)ruthenium(II/III) complexes: A theoretical study

Cited by 12 publications

References 37 publications

Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Preferential Behavior on Donating Atoms of an Ambidentate Ligand 2-Methylisothiazol-3(2H)-one in Its Metal Complexes

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ3N,O:N′]

The RuIVO-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies

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Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]