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

doi:10.1021/ic051487l

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

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

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-[Ru^II(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 Ru^III-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 language	English
Pages (from-to)	1349-1355
Number of pages	7
Journal	Inorganic Chemistry
Volume	45
Issue number	3
DOIs	https://doi.org/10.1021/ic051487l
Publication status	Published - Feb 6 2006
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Dive into the research topics of '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)'. Together they form a unique fingerprint.

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Noda, K., Ohuchi, Y., Hashimoto, A., Fujiki, M., Itoh, S., Iwatsuki, S., Noda, T., Suzuki, T., Kashiwabara, K., & Takagi, H. D. (2006). 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). Inorganic Chemistry, 45(3), 1349-1355. https://doi.org/10.1021/ic051487l

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

Research output: Contribution to journal › Article › peer-review

Noda, K, Ohuchi, Y, Hashimoto, A, Fujiki, M, Itoh, S, Iwatsuki, S, Noda, T, Suzuki, T, Kashiwabara, K & Takagi, HD 2006, '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)', Inorganic Chemistry, vol. 45, no. 3, pp. 1349-1355. https://doi.org/10.1021/ic051487l

Noda K, Ohuchi Y, Hashimoto A, Fujiki M, Itoh S, Iwatsuki S et al. 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). Inorganic Chemistry. 2006 Feb 6;45(3):1349-1355. doi: 10.1021/ic051487l

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title = "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)",

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.}",

year = "2006",

month = feb,

day = "6",

doi = "10.1021/ic051487l",

language = "English",

volume = "45",

pages = "1349--1355",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "3",

}

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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