Interconversion of Persulfido, Sulfur Hydride, and Hydride Ligands Coordinated to CpRu(PPh3)2+

Jayantha Amarasekera; Thomas B. Rauchfuss

doi:10.1021/ic00319a024

Interconversion of Persulfido, Sulfur Hydride, and Hydride Ligands Coordinated to CpRu(PPh₃)₂⁺

Jayantha Amarasekera
, Thomas B. Rauchfuss

Chemistry

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

Abstract

The electron-rich metallothiol CpRu(PPh₃)₂SH (1) has been prepared from the reactions of CpRu(PPh₃)₂Cl with NaSH and CpRu(PPh₃)₂H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh₃)(CO)SH whereas the carbonylation of CpRu(PPh₃)₂Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh₃)₂(SH₂)]⁺. Alkylation of 1 gives thiol complexes [CpRu(PPh₃)₂(RSH)]⁺ (R = CH₃); such complexes were also prepared directly from CpRu(PPh₃)₂OTf (OTf = CF₃SO₃) and RSH. The structure of the thiol complex [CpRu(PPh₃)₂(n-PrSH)]BF₄·CH ₂Cl₂ was determined by X-ray methods. Crystal data: triclinic space group P1, with a = 13.308 (5) Å, b = 14.641 (7) Å, c = 13.205 Å, α = 113.64 (3)°, β = 110.01 (4)°, γ = 84.45 (3)°, V = 2212 (2) Å³, and Z = 2; structure solution and refinement based on 4091 reflections with I > 2.58σ(I) to give R = 0.054. [CpRu(PPh₃)₂(SH₂)]⁺ reacts reversibly with H₂ to give the dihydride [CpRu(PPh₃)₂H₂]⁺. Analogous results were found for [((2-SC₄H₃)CH₂C₅H ₄)Ru(PPh₃)₂]⁺; the S-bound thiophene ligand can be displaced by H₂S, H₂, H^-, and SH^-. [CpRu(PPh₃)₂(H₂S)]⁺ oxidizes in air to give [CpRu(PPh₃)₂]₂(μ-S₂)²⁺ (2). Salts of 2 are formed in two-electron oxidations of 1 with Ph₃CBF₄, Cp₂Fe⁺, and I₂ as well as electrochemically. A presumed intermediate in this oxidation is [CpRu(PPh₃)₂]₂(μ-S₂)⁺. This mixed-valence compound disproportionates upon addition of HOTf to give 2 and [CpRu(PPh₃)₂(SH₂)]⁺. The reaction of 1 with sulfur gave ruthenium polysulfides [CpRu(PPh₃)]₂S_x (x = 4, 6).

Original language	English (US)
Pages (from-to)	3875-3883
Number of pages	9
Journal	Inorganic Chemistry
Volume	28
Issue number	20
DOIs	https://doi.org/10.1021/ic00319a024
State	Published - Oct 1 1989

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{5cc2bc7c31954409b057a4b6e8dc2104,

title = "Interconversion of Persulfido, Sulfur Hydride, and Hydride Ligands Coordinated to CpRu(PPh3)2+",

abstract = "The electron-rich metallothiol CpRu(PPh3)2SH (1) has been prepared from the reactions of CpRu(PPh3)2Cl with NaSH and CpRu(PPh3)2H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh3)(CO)SH whereas the carbonylation of CpRu(PPh3)2Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh3)2(SH2)]+. Alkylation of 1 gives thiol complexes [CpRu(PPh3)2(RSH)]+ (R = CH3); such complexes were also prepared directly from CpRu(PPh3)2OTf (OTf = CF3SO3) and RSH. The structure of the thiol complex [CpRu(PPh3)2(n-PrSH)]BF4·CH 2Cl2 was determined by X-ray methods. Crystal data: triclinic space group P1, with a = 13.308 (5) {\AA}, b = 14.641 (7) {\AA}, c = 13.205 {\AA}, α = 113.64 (3)°, β = 110.01 (4)°, γ = 84.45 (3)°, V = 2212 (2) {\AA}3, and Z = 2; structure solution and refinement based on 4091 reflections with I > 2.58σ(I) to give R = 0.054. [CpRu(PPh3)2(SH2)]+ reacts reversibly with H2 to give the dihydride [CpRu(PPh3)2H2]+. Analogous results were found for [((2-SC4H3)CH2C5H 4)Ru(PPh3)2]+; the S-bound thiophene ligand can be displaced by H2S, H2, H-, and SH-. [CpRu(PPh3)2(H2S)]+ oxidizes in air to give [CpRu(PPh3)2]2(μ-S2)2+ (2). Salts of 2 are formed in two-electron oxidations of 1 with Ph3CBF4, Cp2Fe+, and I2 as well as electrochemically. A presumed intermediate in this oxidation is [CpRu(PPh3)2]2(μ-S2)+. This mixed-valence compound disproportionates upon addition of HOTf to give 2 and [CpRu(PPh3)2(SH2)]+. The reaction of 1 with sulfur gave ruthenium polysulfides [CpRu(PPh3)]2Sx (x = 4, 6).",

author = "Jayantha Amarasekera and Rauchfuss, \{Thomas B.\}",

year = "1989",

month = oct,

day = "1",

doi = "10.1021/ic00319a024",

language = "English (US)",

volume = "28",

pages = "3875--3883",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

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TY - JOUR

T1 - Interconversion of Persulfido, Sulfur Hydride, and Hydride Ligands Coordinated to CpRu(PPh3)2+

AU - Amarasekera, Jayantha

AU - Rauchfuss, Thomas B.

PY - 1989/10/1

Y1 - 1989/10/1

N2 - The electron-rich metallothiol CpRu(PPh3)2SH (1) has been prepared from the reactions of CpRu(PPh3)2Cl with NaSH and CpRu(PPh3)2H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh3)(CO)SH whereas the carbonylation of CpRu(PPh3)2Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh3)2(SH2)]+. Alkylation of 1 gives thiol complexes [CpRu(PPh3)2(RSH)]+ (R = CH3); such complexes were also prepared directly from CpRu(PPh3)2OTf (OTf = CF3SO3) and RSH. The structure of the thiol complex [CpRu(PPh3)2(n-PrSH)]BF4·CH 2Cl2 was determined by X-ray methods. Crystal data: triclinic space group P1, with a = 13.308 (5) Å, b = 14.641 (7) Å, c = 13.205 Å, α = 113.64 (3)°, β = 110.01 (4)°, γ = 84.45 (3)°, V = 2212 (2) Å3, and Z = 2; structure solution and refinement based on 4091 reflections with I > 2.58σ(I) to give R = 0.054. [CpRu(PPh3)2(SH2)]+ reacts reversibly with H2 to give the dihydride [CpRu(PPh3)2H2]+. Analogous results were found for [((2-SC4H3)CH2C5H 4)Ru(PPh3)2]+; the S-bound thiophene ligand can be displaced by H2S, H2, H-, and SH-. [CpRu(PPh3)2(H2S)]+ oxidizes in air to give [CpRu(PPh3)2]2(μ-S2)2+ (2). Salts of 2 are formed in two-electron oxidations of 1 with Ph3CBF4, Cp2Fe+, and I2 as well as electrochemically. A presumed intermediate in this oxidation is [CpRu(PPh3)2]2(μ-S2)+. This mixed-valence compound disproportionates upon addition of HOTf to give 2 and [CpRu(PPh3)2(SH2)]+. The reaction of 1 with sulfur gave ruthenium polysulfides [CpRu(PPh3)]2Sx (x = 4, 6).

AB - The electron-rich metallothiol CpRu(PPh3)2SH (1) has been prepared from the reactions of CpRu(PPh3)2Cl with NaSH and CpRu(PPh3)2H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh3)(CO)SH whereas the carbonylation of CpRu(PPh3)2Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh3)2(SH2)]+. Alkylation of 1 gives thiol complexes [CpRu(PPh3)2(RSH)]+ (R = CH3); such complexes were also prepared directly from CpRu(PPh3)2OTf (OTf = CF3SO3) and RSH. The structure of the thiol complex [CpRu(PPh3)2(n-PrSH)]BF4·CH 2Cl2 was determined by X-ray methods. Crystal data: triclinic space group P1, with a = 13.308 (5) Å, b = 14.641 (7) Å, c = 13.205 Å, α = 113.64 (3)°, β = 110.01 (4)°, γ = 84.45 (3)°, V = 2212 (2) Å3, and Z = 2; structure solution and refinement based on 4091 reflections with I > 2.58σ(I) to give R = 0.054. [CpRu(PPh3)2(SH2)]+ reacts reversibly with H2 to give the dihydride [CpRu(PPh3)2H2]+. Analogous results were found for [((2-SC4H3)CH2C5H 4)Ru(PPh3)2]+; the S-bound thiophene ligand can be displaced by H2S, H2, H-, and SH-. [CpRu(PPh3)2(H2S)]+ oxidizes in air to give [CpRu(PPh3)2]2(μ-S2)2+ (2). Salts of 2 are formed in two-electron oxidations of 1 with Ph3CBF4, Cp2Fe+, and I2 as well as electrochemically. A presumed intermediate in this oxidation is [CpRu(PPh3)2]2(μ-S2)+. This mixed-valence compound disproportionates upon addition of HOTf to give 2 and [CpRu(PPh3)2(SH2)]+. The reaction of 1 with sulfur gave ruthenium polysulfides [CpRu(PPh3)]2Sx (x = 4, 6).

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JO - Inorganic Chemistry

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