Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes

Richard Y.C. Shin; Sin Yee Ng; Geok Kheng Tan; Lip Lin Koh; Soo Beng Khoo; Lai Yoong Goh; Richard D. Webster

doi:10.1021/om034189+

Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes

Richard Y.C. Shin, Sin Yee Ng, Geok Kheng Tan, Lip Lin Koh, Soo Beng Khoo, Lai Yoong Goh^*, Richard D. Webster

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

The reaction of [(HMB)Ru^II(κ³SSS′-tpdt)] (1; HMB = η⁶-C₆Me₆; tpdt = S(CH₂CH₂S^-)₂) with 0.5 molar equiv of [Cp*Ru^IIICl₂]₂ (2A; Cp* = η⁵-C₅Me₅) at ambient temperature gives a mixture of products consisting of the dinuclear complex [{Ru^III(μ-1κ³SSS′:2κ²SS-tp dt) Cl₂(CH₃-CN)}Cp*Ru^IIICl] (6; 7%) and trinuclear complexes [{(HMB)Ru^II(μ₃-1κ³SSS′:2κS :3κS-tpdt)}- {Cp*Ru^II(μ-Cl)}₂] (7; 13%) and [{(HMB)Ru^II(μ-1κ³SSS′:2κ²S S-tpdt)} Ru^IIICl(μ-2κ³SSS′:3κ²SS-tp dt){Cp*Ru^IIICl}]Cl (8; 54%). 1 reacts with 1 molar (monomer) equiv of [Ru^II(COD)Cl₂]_n at 80°C to give yellow solids of [(HMB)Ru^II(μ-1κ³SSS′:2κ² SS-tpdt)Ru^II(COD) Cl₂] (10) in 60% yield. [Cp*Ru^III(κ³SSS′-tpdt)] (2) reacts with [Ru^II(COD)Cl₂]_n in refluxing acetonitrile or with (PPh₃)₃Ru^IICl₂ in MeOH at room temperature to give the dark green trinuclear complex [{Cp*Ru^III(μ-1κ³SSS′: 2κ²SS-tpdt)}₂Ru^IICl]Cl (12) in high yield. Treatment of 8, 10, and 12 with NH₄PF₆ in acetonitrile results in facile replacement of one or two chloro ligands with solvent molecules, giving PF₆^- salts of the chloro-bridged species [{(HMB)Ru^II(μ-1κ³SSS′: 2κ²SS-tpdt)}Ru^III(μ-2κ³ SSS′:3κ²SS-tpdt){Cp*Ru^III(μ-Cl)}] (PF₆)₂ (9), the bis(acetonitrile) derivative [(HMB)Ru^II(μ-1κ³SSS′:2κ² SS-tpdt)Ru^II(COD)(CH₃CN)₂] (PF₆)₂ (11), and the mono(acetonitrile) derivative [{Cp*Ru^III(μ-1κ³SSS′: 2κ²SS-tpdt)}₂Ru^II(CH₃CN)] (PF₆)₂ (13), respectively. The triruthenium complexes can be electrochemically reduced and oxidized in one and sometimes two successive one-electron steps, with many of the reduced and oxidized species being stable on the cyclic voltammetric time scale at low temperatures (-40°C) in CH₂Cl₂. The location of the redox-active sites and the extent of delocalization in the species with unpaired electrons are discussed. The X-ray crystal structures of 6 and 7 and the PF₆^- salts of 9, 11, and 13 are reported. The molecular structure of 7 exhibits a new μ₃-1κ³SSS′:2κS: 3κS-bonding mode for the tpdt ligand.

Original language	English
Pages (from-to)	547-558
Number of pages	12
Journal	Organometallics
Volume	23
Issue number	3
DOIs	https://doi.org/10.1021/om034189+
Publication status	Published - Feb 2 2004
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{db308dd85a7c487294567b64ebf3146e,

title = "Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes",

abstract = "The reaction of [(HMB)RuII(κ3SSS′-tpdt)] (1; HMB = η6-C6Me6; tpdt = S(CH2CH2S-)2) with 0.5 molar equiv of [Cp*RuIIICl2]2 (2A; Cp* = η5-C5Me5) at ambient temperature gives a mixture of products consisting of the dinuclear complex [{RuIII(μ-1κ3SSS′:2κ2SS-tp dt) Cl2(CH3-CN)}Cp*RuIIICl] (6; 7%) and trinuclear complexes [{(HMB)RuII(μ3-1κ3SSS′:2κS :3κS-tpdt)}- {Cp*RuII(μ-Cl)}2] (7; 13%) and [{(HMB)RuII(μ-1κ3SSS′:2κ2S S-tpdt)} RuIIICl(μ-2κ3SSS′:3κ2SS-tp dt){Cp*RuIIICl}]Cl (8; 54%). 1 reacts with 1 molar (monomer) equiv of [RuII(COD)Cl2]n at 80°C to give yellow solids of [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD) Cl2] (10) in 60% yield. [Cp*RuIII(κ3SSS′-tpdt)] (2) reacts with [RuII(COD)Cl2]n in refluxing acetonitrile or with (PPh3)3RuIICl2 in MeOH at room temperature to give the dark green trinuclear complex [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuIICl]Cl (12) in high yield. Treatment of 8, 10, and 12 with NH4PF6 in acetonitrile results in facile replacement of one or two chloro ligands with solvent molecules, giving PF6- salts of the chloro-bridged species [{(HMB)RuII(μ-1κ3SSS′: 2κ2SS-tpdt)}RuIII(μ-2κ3 SSS′:3κ2SS-tpdt){Cp*RuIII(μ-Cl)}] (PF6)2 (9), the bis(acetonitrile) derivative [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD)(CH3CN)2] (PF6)2 (11), and the mono(acetonitrile) derivative [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuII(CH3CN)] (PF6)2 (13), respectively. The triruthenium complexes can be electrochemically reduced and oxidized in one and sometimes two successive one-electron steps, with many of the reduced and oxidized species being stable on the cyclic voltammetric time scale at low temperatures (-40°C) in CH2Cl2. The location of the redox-active sites and the extent of delocalization in the species with unpaired electrons are discussed. The X-ray crystal structures of 6 and 7 and the PF6- salts of 9, 11, and 13 are reported. The molecular structure of 7 exhibits a new μ3-1κ3SSS′:2κS: 3κS-bonding mode for the tpdt ligand.",

author = "Shin, {Richard Y.C.} and Ng, {Sin Yee} and Tan, {Geok Kheng} and Koh, {Lip Lin} and Khoo, {Soo Beng} and Goh, {Lai Yoong} and Webster, {Richard D.}",

year = "2004",

month = feb,

day = "2",

doi = "10.1021/om034189+",

language = "English",

volume = "23",

pages = "547--558",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "3",

}

TY - JOUR

T1 - Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes

AU - Shin, Richard Y.C.

AU - Ng, Sin Yee

AU - Tan, Geok Kheng

AU - Koh, Lip Lin

AU - Khoo, Soo Beng

AU - Goh, Lai Yoong

AU - Webster, Richard D.

PY - 2004/2/2

Y1 - 2004/2/2

N2 - The reaction of [(HMB)RuII(κ3SSS′-tpdt)] (1; HMB = η6-C6Me6; tpdt = S(CH2CH2S-)2) with 0.5 molar equiv of [Cp*RuIIICl2]2 (2A; Cp* = η5-C5Me5) at ambient temperature gives a mixture of products consisting of the dinuclear complex [{RuIII(μ-1κ3SSS′:2κ2SS-tp dt) Cl2(CH3-CN)}Cp*RuIIICl] (6; 7%) and trinuclear complexes [{(HMB)RuII(μ3-1κ3SSS′:2κS :3κS-tpdt)}- {Cp*RuII(μ-Cl)}2] (7; 13%) and [{(HMB)RuII(μ-1κ3SSS′:2κ2S S-tpdt)} RuIIICl(μ-2κ3SSS′:3κ2SS-tp dt){Cp*RuIIICl}]Cl (8; 54%). 1 reacts with 1 molar (monomer) equiv of [RuII(COD)Cl2]n at 80°C to give yellow solids of [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD) Cl2] (10) in 60% yield. [Cp*RuIII(κ3SSS′-tpdt)] (2) reacts with [RuII(COD)Cl2]n in refluxing acetonitrile or with (PPh3)3RuIICl2 in MeOH at room temperature to give the dark green trinuclear complex [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuIICl]Cl (12) in high yield. Treatment of 8, 10, and 12 with NH4PF6 in acetonitrile results in facile replacement of one or two chloro ligands with solvent molecules, giving PF6- salts of the chloro-bridged species [{(HMB)RuII(μ-1κ3SSS′: 2κ2SS-tpdt)}RuIII(μ-2κ3 SSS′:3κ2SS-tpdt){Cp*RuIII(μ-Cl)}] (PF6)2 (9), the bis(acetonitrile) derivative [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD)(CH3CN)2] (PF6)2 (11), and the mono(acetonitrile) derivative [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuII(CH3CN)] (PF6)2 (13), respectively. The triruthenium complexes can be electrochemically reduced and oxidized in one and sometimes two successive one-electron steps, with many of the reduced and oxidized species being stable on the cyclic voltammetric time scale at low temperatures (-40°C) in CH2Cl2. The location of the redox-active sites and the extent of delocalization in the species with unpaired electrons are discussed. The X-ray crystal structures of 6 and 7 and the PF6- salts of 9, 11, and 13 are reported. The molecular structure of 7 exhibits a new μ3-1κ3SSS′:2κS: 3κS-bonding mode for the tpdt ligand.

AB - The reaction of [(HMB)RuII(κ3SSS′-tpdt)] (1; HMB = η6-C6Me6; tpdt = S(CH2CH2S-)2) with 0.5 molar equiv of [Cp*RuIIICl2]2 (2A; Cp* = η5-C5Me5) at ambient temperature gives a mixture of products consisting of the dinuclear complex [{RuIII(μ-1κ3SSS′:2κ2SS-tp dt) Cl2(CH3-CN)}Cp*RuIIICl] (6; 7%) and trinuclear complexes [{(HMB)RuII(μ3-1κ3SSS′:2κS :3κS-tpdt)}- {Cp*RuII(μ-Cl)}2] (7; 13%) and [{(HMB)RuII(μ-1κ3SSS′:2κ2S S-tpdt)} RuIIICl(μ-2κ3SSS′:3κ2SS-tp dt){Cp*RuIIICl}]Cl (8; 54%). 1 reacts with 1 molar (monomer) equiv of [RuII(COD)Cl2]n at 80°C to give yellow solids of [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD) Cl2] (10) in 60% yield. [Cp*RuIII(κ3SSS′-tpdt)] (2) reacts with [RuII(COD)Cl2]n in refluxing acetonitrile or with (PPh3)3RuIICl2 in MeOH at room temperature to give the dark green trinuclear complex [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuIICl]Cl (12) in high yield. Treatment of 8, 10, and 12 with NH4PF6 in acetonitrile results in facile replacement of one or two chloro ligands with solvent molecules, giving PF6- salts of the chloro-bridged species [{(HMB)RuII(μ-1κ3SSS′: 2κ2SS-tpdt)}RuIII(μ-2κ3 SSS′:3κ2SS-tpdt){Cp*RuIII(μ-Cl)}] (PF6)2 (9), the bis(acetonitrile) derivative [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD)(CH3CN)2] (PF6)2 (11), and the mono(acetonitrile) derivative [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuII(CH3CN)] (PF6)2 (13), respectively. The triruthenium complexes can be electrochemically reduced and oxidized in one and sometimes two successive one-electron steps, with many of the reduced and oxidized species being stable on the cyclic voltammetric time scale at low temperatures (-40°C) in CH2Cl2. The location of the redox-active sites and the extent of delocalization in the species with unpaired electrons are discussed. The X-ray crystal structures of 6 and 7 and the PF6- salts of 9, 11, and 13 are reported. The molecular structure of 7 exhibits a new μ3-1κ3SSS′:2κS: 3κS-bonding mode for the tpdt ligand.

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Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes

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