Synthesis, Structure, and Properties of [CpRu(PR3)2]2(μ-S2)2+. Effects of Strong π-Donation in a Disulfur Complex

Jayantha Amarasekera; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/ic00267a023

Synthesis, Structure, and Properties of [CpRu(PR₃)₂]₂(μ-S₂)²⁺. Effects of Strong π-Donation in a Disulfur Complex

Jayantha Amarasekera
, Thomas B. Rauchfuss
, Scott R. Wilson

Chemistry

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

Abstract

Compounds of the type [CpRu(PR₃)₂]₂(μ-S₂)[BF ₄]₂ were prepared via the unusual reaction of CpRu(PR₃)₂Cl, S₈, and silver salts. Another route to these dimers includes the displacement of dihydrothiophene from [CpRu(PPh₃)₂(SC₄H₆)]⁺ with elemental sulfur. Optical and Raman spectroscopic studies of the dications indicate that their green colors (λ_max = 718 nm) arise from transitions within the Ru₂S₂ core. Cyclic voltammetric measurements indicate that the dication can be oxidized (for the PMe₃ derivative) and, in two well-separated steps, reduced. Salts of [CpRu(PPh₃)₂]₂(μ-S₂)⁺ were prepared via reduction of the dication with Et₃N, benzyl alcohol, or thiophenol. The EPR spectrum of the monocation shows a five-line pattern indicating the equivalency of the four phosphorus centers. The structure of [CpRu(PMe₃)₂]₂(μ-S₂)[BF ₄]₂·2C₆H₅NO₂ was determined by X-ray diffraction. The compound crystallized in the monoclinic space group P2₁/c with a = 8.424 (2) Å, b = 18.117 (5) Å, c = 17.424 (3) Å, and β = 92.13 (2)°. The structure was refined to a final R = 0.053 (R_w = 0.062). The dication is centrosymmetric with short Ru-S (2.208 (3) Å) and S-S (1.962 (4) Å) distances. The structure, electrochemistry, and stoichiometry of the dication indicate a delocalized, multiply bonded Ru..^-S..^-S..^-Ru core.

Original language	English (US)
Pages (from-to)	3328-3332
Number of pages	5
Journal	Inorganic Chemistry
Volume	26
Issue number	20
DOIs	https://doi.org/10.1021/ic00267a023
State	Published - Oct 1 1987

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{86354b15cd004b2486b8fbc1408f2b40,

title = "Synthesis, Structure, and Properties of [CpRu(PR3)2]2(μ-S2)2+. Effects of Strong π-Donation in a Disulfur Complex",

abstract = "Compounds of the type [CpRu(PR3)2]2(μ-S2)[BF 4]2 were prepared via the unusual reaction of CpRu(PR3)2Cl, S8, and silver salts. Another route to these dimers includes the displacement of dihydrothiophene from [CpRu(PPh3)2(SC4H6)]+ with elemental sulfur. Optical and Raman spectroscopic studies of the dications indicate that their green colors (λmax = 718 nm) arise from transitions within the Ru2S2 core. Cyclic voltammetric measurements indicate that the dication can be oxidized (for the PMe3 derivative) and, in two well-separated steps, reduced. Salts of [CpRu(PPh3)2]2(μ-S2)+ were prepared via reduction of the dication with Et3N, benzyl alcohol, or thiophenol. The EPR spectrum of the monocation shows a five-line pattern indicating the equivalency of the four phosphorus centers. The structure of [CpRu(PMe3)2]2(μ-S2)[BF 4]2·2C6H5NO2 was determined by X-ray diffraction. The compound crystallized in the monoclinic space group P21/c with a = 8.424 (2) {\AA}, b = 18.117 (5) {\AA}, c = 17.424 (3) {\AA}, and β = 92.13 (2)°. The structure was refined to a final R = 0.053 (Rw = 0.062). The dication is centrosymmetric with short Ru-S (2.208 (3) {\AA}) and S-S (1.962 (4) {\AA}) distances. The structure, electrochemistry, and stoichiometry of the dication indicate a delocalized, multiply bonded Ru..-S..-S..-Ru core.",

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

year = "1987",

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T1 - Synthesis, Structure, and Properties of [CpRu(PR3)2]2(μ-S2)2+. Effects of Strong π-Donation in a Disulfur Complex

AU - Amarasekera, Jayantha

AU - Rauchfuss, Thomas B.

AU - Wilson, Scott R.

PY - 1987/10/1

Y1 - 1987/10/1

N2 - Compounds of the type [CpRu(PR3)2]2(μ-S2)[BF 4]2 were prepared via the unusual reaction of CpRu(PR3)2Cl, S8, and silver salts. Another route to these dimers includes the displacement of dihydrothiophene from [CpRu(PPh3)2(SC4H6)]+ with elemental sulfur. Optical and Raman spectroscopic studies of the dications indicate that their green colors (λmax = 718 nm) arise from transitions within the Ru2S2 core. Cyclic voltammetric measurements indicate that the dication can be oxidized (for the PMe3 derivative) and, in two well-separated steps, reduced. Salts of [CpRu(PPh3)2]2(μ-S2)+ were prepared via reduction of the dication with Et3N, benzyl alcohol, or thiophenol. The EPR spectrum of the monocation shows a five-line pattern indicating the equivalency of the four phosphorus centers. The structure of [CpRu(PMe3)2]2(μ-S2)[BF 4]2·2C6H5NO2 was determined by X-ray diffraction. The compound crystallized in the monoclinic space group P21/c with a = 8.424 (2) Å, b = 18.117 (5) Å, c = 17.424 (3) Å, and β = 92.13 (2)°. The structure was refined to a final R = 0.053 (Rw = 0.062). The dication is centrosymmetric with short Ru-S (2.208 (3) Å) and S-S (1.962 (4) Å) distances. The structure, electrochemistry, and stoichiometry of the dication indicate a delocalized, multiply bonded Ru..-S..-S..-Ru core.

AB - Compounds of the type [CpRu(PR3)2]2(μ-S2)[BF 4]2 were prepared via the unusual reaction of CpRu(PR3)2Cl, S8, and silver salts. Another route to these dimers includes the displacement of dihydrothiophene from [CpRu(PPh3)2(SC4H6)]+ with elemental sulfur. Optical and Raman spectroscopic studies of the dications indicate that their green colors (λmax = 718 nm) arise from transitions within the Ru2S2 core. Cyclic voltammetric measurements indicate that the dication can be oxidized (for the PMe3 derivative) and, in two well-separated steps, reduced. Salts of [CpRu(PPh3)2]2(μ-S2)+ were prepared via reduction of the dication with Et3N, benzyl alcohol, or thiophenol. The EPR spectrum of the monocation shows a five-line pattern indicating the equivalency of the four phosphorus centers. The structure of [CpRu(PMe3)2]2(μ-S2)[BF 4]2·2C6H5NO2 was determined by X-ray diffraction. The compound crystallized in the monoclinic space group P21/c with a = 8.424 (2) Å, b = 18.117 (5) Å, c = 17.424 (3) Å, and β = 92.13 (2)°. The structure was refined to a final R = 0.053 (Rw = 0.062). The dication is centrosymmetric with short Ru-S (2.208 (3) Å) and S-S (1.962 (4) Å) distances. The structure, electrochemistry, and stoichiometry of the dication indicate a delocalized, multiply bonded Ru..-S..-S..-Ru core.

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