Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*RuIVCl 2(S2CR)] (Cp* = η5-C 5Me5, R = NMe2, NEt2, O iPr)

Seah Ling Kuan; Elaine Phuay Leng Tay; Weng Kee Leong; Lai Yoong Goh; Ching Yeh Lin; Peter M.W. Gill; Richard D. Webster

doi:10.1021/om060866z

Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [CpRu^IVCl ₂(S₂CR)] (Cp = η⁵-C ₅Me₅, R = NMe₂, NEt₂, O ⁱPr)

Seah Ling Kuan, Elaine Phuay Leng Tay, Weng Kee Leong, Lai Yoong Goh^*, Ching Yeh Lin, Peter M.W. Gill, Richard D. Webster

^*Corresponding author for this work

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Abstract

[Cp*Ru^IVCl₂(S₂CR)] (R = NMe ₂, NEt₂, OⁱPr) were synthesized by the reaction of [Cp*Ru^IIICl₂]₂ with [RC(S)S] ₂. One-electron electrochemical oxidation of [Cp*RuCl ₂(S₂CR)] produces paramagnetic [Cp*RuCl ₂(S₂CR)]⁺, which are stable in CH ₂Cl₂ solution for at least several hours at 233 K. EPR experiments performed at 293 K show isotropic signals (g ≈ 2.035) with clearly defined hyperfine coupling to ⁹⁹Ru and ¹⁰¹Ru of 25 G and with peak-to-peak line widths of 15 G. At temperatures below 153 K, axial-shaped EPR spectra were obtained with g-values close to 2 (2.050-2.008) and narrow peak-to-peak line widths (15 G). Results from DFT calculations indicate that approximately 70% of the spin density in [Cp*RuCl ₂(S₂CNMe₂)]⁺ is located on the ruthenium, although there is an increase of only 0.06 in the positive charge of the metal ion as a result of the oxidation. The high spin density on Ru supports the assignment of a formally Ru(V) oxidation state, which is unprecedented in organometallic chemistry. Chemical oxidation of Cp*Ru^IVCl ₂(S₂CNMe₂) with NO(PF₆) in CH ₃CN resulted in the isolation of [Cp*Ru^IV(MeCN) ₂(S₂CNMe₂)]⁺² (4), while oxidation with [(4-Br-C₆H₄)₃N](SbCl₆) in CH₂Cl₂ resulted in the formation of chloro-bridged dimeric [Cp*Ru^IVCl(S₂CNMe₂)]₂ ⁺² (5). When 5 is dissolved in CD₃-CN/CH₃CN, it immediately converts to 4. Cyclic voltammetric experiments confirmed that in both solvents the chemical oxidation process occurred through the [Cp*Ru^vCl₂(S₂CNMe₂)] ⁺ intermediate.

Original language	English
Pages (from-to)	6134-6141
Number of pages	8
Journal	Organometallics
Volume	25
Issue number	26
DOIs	https://doi.org/10.1021/om060866z
Publication status	Published - 18 Dec 2006

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@article{b5794a9442ea47aba20d1341a0ffc856,

title = "Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*RuIVCl 2(S2CR)] (Cp* = η5-C 5Me5, R = NMe2, NEt2, O iPr)",

abstract = "[Cp*RuIVCl2(S2CR)] (R = NMe 2, NEt2, OiPr) were synthesized by the reaction of [Cp*RuIIICl2]2 with [RC(S)S] 2. One-electron electrochemical oxidation of [Cp*RuCl 2(S2CR)] produces paramagnetic [Cp*RuCl 2(S2CR)]+, which are stable in CH 2Cl2 solution for at least several hours at 233 K. EPR experiments performed at 293 K show isotropic signals (g ≈ 2.035) with clearly defined hyperfine coupling to 99Ru and 101Ru of 25 G and with peak-to-peak line widths of 15 G. At temperatures below 153 K, axial-shaped EPR spectra were obtained with g-values close to 2 (2.050-2.008) and narrow peak-to-peak line widths (15 G). Results from DFT calculations indicate that approximately 70% of the spin density in [Cp*RuCl 2(S2CNMe2)]+ is located on the ruthenium, although there is an increase of only 0.06 in the positive charge of the metal ion as a result of the oxidation. The high spin density on Ru supports the assignment of a formally Ru(V) oxidation state, which is unprecedented in organometallic chemistry. Chemical oxidation of Cp*RuIVCl 2(S2CNMe2) with NO(PF6) in CH 3CN resulted in the isolation of [Cp*RuIV(MeCN) 2(S2CNMe2)]+2 (4), while oxidation with [(4-Br-C6H4)3N](SbCl6) in CH2Cl2 resulted in the formation of chloro-bridged dimeric [Cp*RuIVCl(S2CNMe2)]2 +2 (5). When 5 is dissolved in CD3-CN/CH3CN, it immediately converts to 4. Cyclic voltammetric experiments confirmed that in both solvents the chemical oxidation process occurred through the [Cp*RuvCl2(S2CNMe2)] + intermediate.",

author = "Kuan, {Seah Ling} and Tay, {Elaine Phuay Leng} and Leong, {Weng Kee} and Goh, {Lai Yoong} and Lin, {Ching Yeh} and Gill, {Peter M.W.} and Webster, {Richard D.}",

year = "2006",

month = dec,

day = "18",

doi = "10.1021/om060866z",

language = "English",

volume = "25",

pages = "6134--6141",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "26",

}

Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*Ru^IVCl ₂(S₂CR)] (Cp* = η⁵-C ₅Me₅, R = NMe₂, NEt₂, O ⁱPr). / Kuan, Seah Ling; Tay, Elaine Phuay Leng; Leong, Weng Kee et al.
In: Organometallics, Vol. 25, No. 26, 18.12.2006, p. 6134-6141.

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

TY - JOUR

T1 - Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*RuIVCl 2(S2CR)] (Cp* = η5-C 5Me5, R = NMe2, NEt2, O iPr)

AU - Kuan, Seah Ling

AU - Tay, Elaine Phuay Leng

AU - Leong, Weng Kee

AU - Goh, Lai Yoong

AU - Lin, Ching Yeh

AU - Gill, Peter M.W.

AU - Webster, Richard D.

PY - 2006/12/18

Y1 - 2006/12/18

N2 - [Cp*RuIVCl2(S2CR)] (R = NMe 2, NEt2, OiPr) were synthesized by the reaction of [Cp*RuIIICl2]2 with [RC(S)S] 2. One-electron electrochemical oxidation of [Cp*RuCl 2(S2CR)] produces paramagnetic [Cp*RuCl 2(S2CR)]+, which are stable in CH 2Cl2 solution for at least several hours at 233 K. EPR experiments performed at 293 K show isotropic signals (g ≈ 2.035) with clearly defined hyperfine coupling to 99Ru and 101Ru of 25 G and with peak-to-peak line widths of 15 G. At temperatures below 153 K, axial-shaped EPR spectra were obtained with g-values close to 2 (2.050-2.008) and narrow peak-to-peak line widths (15 G). Results from DFT calculations indicate that approximately 70% of the spin density in [Cp*RuCl 2(S2CNMe2)]+ is located on the ruthenium, although there is an increase of only 0.06 in the positive charge of the metal ion as a result of the oxidation. The high spin density on Ru supports the assignment of a formally Ru(V) oxidation state, which is unprecedented in organometallic chemistry. Chemical oxidation of Cp*RuIVCl 2(S2CNMe2) with NO(PF6) in CH 3CN resulted in the isolation of [Cp*RuIV(MeCN) 2(S2CNMe2)]+2 (4), while oxidation with [(4-Br-C6H4)3N](SbCl6) in CH2Cl2 resulted in the formation of chloro-bridged dimeric [Cp*RuIVCl(S2CNMe2)]2 +2 (5). When 5 is dissolved in CD3-CN/CH3CN, it immediately converts to 4. Cyclic voltammetric experiments confirmed that in both solvents the chemical oxidation process occurred through the [Cp*RuvCl2(S2CNMe2)] + intermediate.

AB - [Cp*RuIVCl2(S2CR)] (R = NMe 2, NEt2, OiPr) were synthesized by the reaction of [Cp*RuIIICl2]2 with [RC(S)S] 2. One-electron electrochemical oxidation of [Cp*RuCl 2(S2CR)] produces paramagnetic [Cp*RuCl 2(S2CR)]+, which are stable in CH 2Cl2 solution for at least several hours at 233 K. EPR experiments performed at 293 K show isotropic signals (g ≈ 2.035) with clearly defined hyperfine coupling to 99Ru and 101Ru of 25 G and with peak-to-peak line widths of 15 G. At temperatures below 153 K, axial-shaped EPR spectra were obtained with g-values close to 2 (2.050-2.008) and narrow peak-to-peak line widths (15 G). Results from DFT calculations indicate that approximately 70% of the spin density in [Cp*RuCl 2(S2CNMe2)]+ is located on the ruthenium, although there is an increase of only 0.06 in the positive charge of the metal ion as a result of the oxidation. The high spin density on Ru supports the assignment of a formally Ru(V) oxidation state, which is unprecedented in organometallic chemistry. Chemical oxidation of Cp*RuIVCl 2(S2CNMe2) with NO(PF6) in CH 3CN resulted in the isolation of [Cp*RuIV(MeCN) 2(S2CNMe2)]+2 (4), while oxidation with [(4-Br-C6H4)3N](SbCl6) in CH2Cl2 resulted in the formation of chloro-bridged dimeric [Cp*RuIVCl(S2CNMe2)]2 +2 (5). When 5 is dissolved in CD3-CN/CH3CN, it immediately converts to 4. Cyclic voltammetric experiments confirmed that in both solvents the chemical oxidation process occurred through the [Cp*RuvCl2(S2CNMe2)] + intermediate.

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U2 - 10.1021/om060866z

DO - 10.1021/om060866z

M3 - Article

SN - 0276-7333

VL - 25

SP - 6134

EP - 6141

JO - Organometallics

JF - Organometallics

IS - 26

ER -

Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [CpRu^IVCl ₂(S₂CR)] (Cp = η⁵-C ₅Me₅, R = NMe₂, NEt₂, O ⁱPr)

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