Syntheses, structural determinations of [Ru(ROCS2) 2(PPh3)2]+/0 pairs, and kinetic analyses of thermal reactions involving transient trans-[Ru( iPrOCS2)2(PPh3)2] species (ROCS2- = ethyl- or isopropyldithiocarbonate and PPh3 = triphenylphosphine)

Kyoko Noda, Yuko Ohuchi, Akira Hashimoto, Masayuki Fujiki, Sumitaka Itoh, Satoshi Iwatsuki, Toshiaki Noda, Takayoshi Suzuki, Kazuo Kashiwabara, Hideo D. Takagi

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Abstract

Controlled-potential electrochemical oxidation of cis-[Ru(ROCS 2)2(PPh3)2] (R = Et, iPr) yielded corresponding Ru(III) complexes, and the crystal structures of cis-[Ru(ROCS2)2(PPh3)2] and trans-[Ru(ROCS2)2(PPh3)2](PF 6) were determined. Both pairs of complexes exhibited almost identical coordination structures. The Ru-P distances in trans-[Ru III(ROCS2)2(PPh3) 2](PF6) [2.436(3)-2.443(3) Å] were significantly longer than those in cis-[RuII(ROCS2)2- (PPh3)2] [2.306(1)-2.315(2) Å]: the smaller ionic radius of Ru(III) than that of Ru(II) stabilizes the trans conformation for the Ru(III) complex due to the steric requirement of bulky phosphine ligands while mutual trans influence by the phosphine ligands induces significant elongation of the RuIII-P bonds. Cyclic voltammograms of the cis-[Ru(ROCS 2)2-(PPh3)2] and trans-[Ru(ROCS 2)2(PPh3)2]+ complexes in dichloromethane solution exhibited typical dual redox signals corresponding to the cis-[Ru(ROCS2)2(PPh3)2] +/0 (ca. +0.15 and +0.10 V vs ferrocenium/ferrocene couple for R = Et and iPr, respectively) and to trans-[Ru(ROCS2) 2(PPh3)2]+/0 (-0.05 and -0.15 V vs ferrocenium/ferrocene for R = Et and iPr, respectively) couples. Analyses on the basis of the Nicholson and Shain's method revealed that the thermal disappearance rate of transient trans-[Ru(ROCS2) 2(PPh3)2] was dependent on the concentration of PPh3 in the bulk: the rate constant for the intramolecular isomerization reaction of trans-[Ru(iPrOCS2) 2(PPh3)2] was determined as 0.338 ± 0.004 s-1 at 298.3 K (ΔH* = 41.8 ± 1.5 kJ mol -1 and ΔS* = -114 ± 7 J mol-1 K -1), while the dissociation rate constant of coordinated PPh 3 from the trans-[Ru(iPrOCS2) 2(PPh3)2] species was estimated as 0.113 ± 0.008 s-1 at 298.3 K (ΔH* = 97.6 ± 0.8 kJ mol-1 and ΔS* = 64 ± 3 J mol-1 K -1), by monitoring the EC reaction (electrode reaction followed by chemical processes) at different concentrations of PPh3 in the bulk. It was found that the trans to cis isomerization reaction takes place via the partial dissociation of iPrOCS2- from Ru(II), contrary to the previous claim that it takes place by the twist mechanism.

Original languageEnglish
Pages (from-to)1349-1355
Number of pages7
JournalInorganic Chemistry
Volume45
Issue number3
DOIs
Publication statusPublished - Feb 6 2006
Externally publishedYes

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phosphine
Kinetics
kinetics
synthesis
phosphines
isomerization
dissociation
ligands
electrochemical oxidation
Isomerization
elongation
Rate constants
Ligands
requirements
crystal structure
radii
electrodes
dichlorotetrakis(dimethyl sulfoxide)ruthenium II
Hot Temperature
triphenylphosphine

ASJC Scopus subject areas

  • Inorganic Chemistry

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Syntheses, structural determinations of [Ru(ROCS2) 2(PPh3)2]+/0 pairs, and kinetic analyses of thermal reactions involving transient trans-[Ru( iPrOCS2)2(PPh3)2] species (ROCS2- = ethyl- or isopropyldithiocarbonate and PPh3 = triphenylphosphine). / Noda, Kyoko; Ohuchi, Yuko; Hashimoto, Akira; Fujiki, Masayuki; Itoh, Sumitaka; Iwatsuki, Satoshi; Noda, Toshiaki; Suzuki, Takayoshi; Kashiwabara, Kazuo; Takagi, Hideo D.

In: Inorganic Chemistry, Vol. 45, No. 3, 06.02.2006, p. 1349-1355.

Research output: Contribution to journalArticle

Noda, Kyoko ; Ohuchi, Yuko ; Hashimoto, Akira ; Fujiki, Masayuki ; Itoh, Sumitaka ; Iwatsuki, Satoshi ; Noda, Toshiaki ; Suzuki, Takayoshi ; Kashiwabara, Kazuo ; Takagi, Hideo D. / Syntheses, structural determinations of [Ru(ROCS2) 2(PPh3)2]+/0 pairs, and kinetic analyses of thermal reactions involving transient trans-[Ru( iPrOCS2)2(PPh3)2] species (ROCS2- = ethyl- or isopropyldithiocarbonate and PPh3 = triphenylphosphine). In: Inorganic Chemistry. 2006 ; Vol. 45, No. 3. pp. 1349-1355.
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abstract = "Controlled-potential electrochemical oxidation of cis-[Ru(ROCS 2)2(PPh3)2] (R = Et, iPr) yielded corresponding Ru(III) complexes, and the crystal structures of cis-[Ru(ROCS2)2(PPh3)2] and trans-[Ru(ROCS2)2(PPh3)2](PF 6) were determined. Both pairs of complexes exhibited almost identical coordination structures. The Ru-P distances in trans-[Ru III(ROCS2)2(PPh3) 2](PF6) [2.436(3)-2.443(3) {\AA}] were significantly longer than those in cis-[RuII(ROCS2)2- (PPh3)2] [2.306(1)-2.315(2) {\AA}]: the smaller ionic radius of Ru(III) than that of Ru(II) stabilizes the trans conformation for the Ru(III) complex due to the steric requirement of bulky phosphine ligands while mutual trans influence by the phosphine ligands induces significant elongation of the RuIII-P bonds. Cyclic voltammograms of the cis-[Ru(ROCS 2)2-(PPh3)2] and trans-[Ru(ROCS 2)2(PPh3)2]+ complexes in dichloromethane solution exhibited typical dual redox signals corresponding to the cis-[Ru(ROCS2)2(PPh3)2] +/0 (ca. +0.15 and +0.10 V vs ferrocenium/ferrocene couple for R = Et and iPr, respectively) and to trans-[Ru(ROCS2) 2(PPh3)2]+/0 (-0.05 and -0.15 V vs ferrocenium/ferrocene for R = Et and iPr, respectively) couples. Analyses on the basis of the Nicholson and Shain's method revealed that the thermal disappearance rate of transient trans-[Ru(ROCS2) 2(PPh3)2] was dependent on the concentration of PPh3 in the bulk: the rate constant for the intramolecular isomerization reaction of trans-[Ru(iPrOCS2) 2(PPh3)2] was determined as 0.338 ± 0.004 s-1 at 298.3 K (ΔH* = 41.8 ± 1.5 kJ mol -1 and ΔS* = -114 ± 7 J mol-1 K -1), while the dissociation rate constant of coordinated PPh 3 from the trans-[Ru(iPrOCS2) 2(PPh3)2] species was estimated as 0.113 ± 0.008 s-1 at 298.3 K (ΔH* = 97.6 ± 0.8 kJ mol-1 and ΔS* = 64 ± 3 J mol-1 K -1), by monitoring the EC reaction (electrode reaction followed by chemical processes) at different concentrations of PPh3 in the bulk. It was found that the trans to cis isomerization reaction takes place via the partial dissociation of iPrOCS2- from Ru(II), contrary to the previous claim that it takes place by the twist mechanism.",
author = "Kyoko Noda and Yuko Ohuchi and Akira Hashimoto and Masayuki Fujiki and Sumitaka Itoh and Satoshi Iwatsuki and Toshiaki Noda and Takayoshi Suzuki and Kazuo Kashiwabara and Takagi, {Hideo D.}",
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TY - JOUR

T1 - Syntheses, structural determinations of [Ru(ROCS2) 2(PPh3)2]+/0 pairs, and kinetic analyses of thermal reactions involving transient trans-[Ru( iPrOCS2)2(PPh3)2] species (ROCS2- = ethyl- or isopropyldithiocarbonate and PPh3 = triphenylphosphine)

AU - Noda, Kyoko

AU - Ohuchi, Yuko

AU - Hashimoto, Akira

AU - Fujiki, Masayuki

AU - Itoh, Sumitaka

AU - Iwatsuki, Satoshi

AU - Noda, Toshiaki

AU - Suzuki, Takayoshi

AU - Kashiwabara, Kazuo

AU - Takagi, Hideo D.

PY - 2006/2/6

Y1 - 2006/2/6

N2 - Controlled-potential electrochemical oxidation of cis-[Ru(ROCS 2)2(PPh3)2] (R = Et, iPr) yielded corresponding Ru(III) complexes, and the crystal structures of cis-[Ru(ROCS2)2(PPh3)2] and trans-[Ru(ROCS2)2(PPh3)2](PF 6) were determined. Both pairs of complexes exhibited almost identical coordination structures. The Ru-P distances in trans-[Ru III(ROCS2)2(PPh3) 2](PF6) [2.436(3)-2.443(3) Å] were significantly longer than those in cis-[RuII(ROCS2)2- (PPh3)2] [2.306(1)-2.315(2) Å]: the smaller ionic radius of Ru(III) than that of Ru(II) stabilizes the trans conformation for the Ru(III) complex due to the steric requirement of bulky phosphine ligands while mutual trans influence by the phosphine ligands induces significant elongation of the RuIII-P bonds. Cyclic voltammograms of the cis-[Ru(ROCS 2)2-(PPh3)2] and trans-[Ru(ROCS 2)2(PPh3)2]+ complexes in dichloromethane solution exhibited typical dual redox signals corresponding to the cis-[Ru(ROCS2)2(PPh3)2] +/0 (ca. +0.15 and +0.10 V vs ferrocenium/ferrocene couple for R = Et and iPr, respectively) and to trans-[Ru(ROCS2) 2(PPh3)2]+/0 (-0.05 and -0.15 V vs ferrocenium/ferrocene for R = Et and iPr, respectively) couples. Analyses on the basis of the Nicholson and Shain's method revealed that the thermal disappearance rate of transient trans-[Ru(ROCS2) 2(PPh3)2] was dependent on the concentration of PPh3 in the bulk: the rate constant for the intramolecular isomerization reaction of trans-[Ru(iPrOCS2) 2(PPh3)2] was determined as 0.338 ± 0.004 s-1 at 298.3 K (ΔH* = 41.8 ± 1.5 kJ mol -1 and ΔS* = -114 ± 7 J mol-1 K -1), while the dissociation rate constant of coordinated PPh 3 from the trans-[Ru(iPrOCS2) 2(PPh3)2] species was estimated as 0.113 ± 0.008 s-1 at 298.3 K (ΔH* = 97.6 ± 0.8 kJ mol-1 and ΔS* = 64 ± 3 J mol-1 K -1), by monitoring the EC reaction (electrode reaction followed by chemical processes) at different concentrations of PPh3 in the bulk. It was found that the trans to cis isomerization reaction takes place via the partial dissociation of iPrOCS2- from Ru(II), contrary to the previous claim that it takes place by the twist mechanism.

AB - Controlled-potential electrochemical oxidation of cis-[Ru(ROCS 2)2(PPh3)2] (R = Et, iPr) yielded corresponding Ru(III) complexes, and the crystal structures of cis-[Ru(ROCS2)2(PPh3)2] and trans-[Ru(ROCS2)2(PPh3)2](PF 6) were determined. Both pairs of complexes exhibited almost identical coordination structures. The Ru-P distances in trans-[Ru III(ROCS2)2(PPh3) 2](PF6) [2.436(3)-2.443(3) Å] were significantly longer than those in cis-[RuII(ROCS2)2- (PPh3)2] [2.306(1)-2.315(2) Å]: the smaller ionic radius of Ru(III) than that of Ru(II) stabilizes the trans conformation for the Ru(III) complex due to the steric requirement of bulky phosphine ligands while mutual trans influence by the phosphine ligands induces significant elongation of the RuIII-P bonds. Cyclic voltammograms of the cis-[Ru(ROCS 2)2-(PPh3)2] and trans-[Ru(ROCS 2)2(PPh3)2]+ complexes in dichloromethane solution exhibited typical dual redox signals corresponding to the cis-[Ru(ROCS2)2(PPh3)2] +/0 (ca. +0.15 and +0.10 V vs ferrocenium/ferrocene couple for R = Et and iPr, respectively) and to trans-[Ru(ROCS2) 2(PPh3)2]+/0 (-0.05 and -0.15 V vs ferrocenium/ferrocene for R = Et and iPr, respectively) couples. Analyses on the basis of the Nicholson and Shain's method revealed that the thermal disappearance rate of transient trans-[Ru(ROCS2) 2(PPh3)2] was dependent on the concentration of PPh3 in the bulk: the rate constant for the intramolecular isomerization reaction of trans-[Ru(iPrOCS2) 2(PPh3)2] was determined as 0.338 ± 0.004 s-1 at 298.3 K (ΔH* = 41.8 ± 1.5 kJ mol -1 and ΔS* = -114 ± 7 J mol-1 K -1), while the dissociation rate constant of coordinated PPh 3 from the trans-[Ru(iPrOCS2) 2(PPh3)2] species was estimated as 0.113 ± 0.008 s-1 at 298.3 K (ΔH* = 97.6 ± 0.8 kJ mol-1 and ΔS* = 64 ± 3 J mol-1 K -1), by monitoring the EC reaction (electrode reaction followed by chemical processes) at different concentrations of PPh3 in the bulk. It was found that the trans to cis isomerization reaction takes place via the partial dissociation of iPrOCS2- from Ru(II), contrary to the previous claim that it takes place by the twist mechanism.

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DO - 10.1021/ic051487l

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JF - Inorganic Chemistry

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