The Chemistry of (ring)Ru2+ (ring = Tetramethylthiophene, p-Cymene)

Edward A. Ganja; Thomas B. Rauchfuss; Charlotte L. Stern

doi:10.1021/om00047a060

The Chemistry of (ring)Ru²⁺ (ring = Tetramethylthiophene, p-Cymene)

Edward A. Ganja, Thomas B. Rauchfuss, Charlotte L. Stern

Chemistry

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

Abstract

Described are the compounds [(ring)Ru(OTf)₂]_x, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to [(ring)RuL₃]²⁺, where L₃ = (H₂O)₃, (NH₃)₃, and (PH₃)₃. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf)₂. The addition of thiophenes to CH₂Cl₂ solutions of 1 or 2 leads to the precipitation of the sandwich compounds [(ring)(SC₄R₄)Ru](OTf)₂, where SC₄R₄ = thiophene, 2,5-dimethylthiophene, and TMT. [(TMT)Ru-(H₂O)₃](OTf)₂ was characterized by single-crystal X-ray crystallography, which established a piano-stool geometry with a planar TMT ligand. [(TMT)Ru(D₂O)₃](OTf)₂ decomposes in D₂O solution at 150°C to give [(TMT)₂Ru]²⁺, which undergoes selective deuteration at the 2,5-methyl groups. D₂O solutions of [(TMT)₂Ru]²⁺ undergo photochemical loss of one TMT ligand in water to give [(TMT)Ru(D₂O)₃]²⁺. Photolysis of an aqueous solution of [(TMT)(p-cymene)Ru]²⁺ gives primarily [(TMT)Ru(H₂O)₃]²⁺. A procedure is described for the reversible loading of 1 onto γ-alumina, which in turn was characterized by ¹³C CP-MAS NMR spectroscopy.

Original language	English (US)
Pages (from-to)	270-275
Number of pages	6
Journal	Organometallics
Volume	10
Issue number	1
DOIs	https://doi.org/10.1021/om00047a060
State	Published - Jan 1 1991

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00047a060

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@article{2b7ef852176d4e58b445ef653e81c176,

title = "The Chemistry of (ring)Ru2+ (ring = Tetramethylthiophene, p-Cymene)",

abstract = "Described are the compounds [(ring)Ru(OTf)2]x, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to [(ring)RuL3]2+, where L3 = (H2O)3, (NH3)3, and (PH3)3. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf)2. The addition of thiophenes to CH2Cl2 solutions of 1 or 2 leads to the precipitation of the sandwich compounds [(ring)(SC4R4)Ru](OTf)2, where SC4R4 = thiophene, 2,5-dimethylthiophene, and TMT. [(TMT)Ru-(H2O)3](OTf)2 was characterized by single-crystal X-ray crystallography, which established a piano-stool geometry with a planar TMT ligand. [(TMT)Ru(D2O)3](OTf)2 decomposes in D2O solution at 150°C to give [(TMT)2Ru]2+, which undergoes selective deuteration at the 2,5-methyl groups. D2O solutions of [(TMT)2Ru]2+ undergo photochemical loss of one TMT ligand in water to give [(TMT)Ru(D2O)3]2+. Photolysis of an aqueous solution of [(TMT)(p-cymene)Ru]2+ gives primarily [(TMT)Ru(H2O)3]2+. A procedure is described for the reversible loading of 1 onto γ-alumina, which in turn was characterized by 13C CP-MAS NMR spectroscopy.",

author = "Ganja, {Edward A.} and Rauchfuss, {Thomas B.} and Stern, {Charlotte L.}",

year = "1991",

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language = "English (US)",

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T1 - The Chemistry of (ring)Ru2+ (ring = Tetramethylthiophene, p-Cymene)

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N2 - Described are the compounds [(ring)Ru(OTf)2]x, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to [(ring)RuL3]2+, where L3 = (H2O)3, (NH3)3, and (PH3)3. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf)2. The addition of thiophenes to CH2Cl2 solutions of 1 or 2 leads to the precipitation of the sandwich compounds [(ring)(SC4R4)Ru](OTf)2, where SC4R4 = thiophene, 2,5-dimethylthiophene, and TMT. [(TMT)Ru-(H2O)3](OTf)2 was characterized by single-crystal X-ray crystallography, which established a piano-stool geometry with a planar TMT ligand. [(TMT)Ru(D2O)3](OTf)2 decomposes in D2O solution at 150°C to give [(TMT)2Ru]2+, which undergoes selective deuteration at the 2,5-methyl groups. D2O solutions of [(TMT)2Ru]2+ undergo photochemical loss of one TMT ligand in water to give [(TMT)Ru(D2O)3]2+. Photolysis of an aqueous solution of [(TMT)(p-cymene)Ru]2+ gives primarily [(TMT)Ru(H2O)3]2+. A procedure is described for the reversible loading of 1 onto γ-alumina, which in turn was characterized by 13C CP-MAS NMR spectroscopy.

AB - Described are the compounds [(ring)Ru(OTf)2]x, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to [(ring)RuL3]2+, where L3 = (H2O)3, (NH3)3, and (PH3)3. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf)2. The addition of thiophenes to CH2Cl2 solutions of 1 or 2 leads to the precipitation of the sandwich compounds [(ring)(SC4R4)Ru](OTf)2, where SC4R4 = thiophene, 2,5-dimethylthiophene, and TMT. [(TMT)Ru-(H2O)3](OTf)2 was characterized by single-crystal X-ray crystallography, which established a piano-stool geometry with a planar TMT ligand. [(TMT)Ru(D2O)3](OTf)2 decomposes in D2O solution at 150°C to give [(TMT)2Ru]2+, which undergoes selective deuteration at the 2,5-methyl groups. D2O solutions of [(TMT)2Ru]2+ undergo photochemical loss of one TMT ligand in water to give [(TMT)Ru(D2O)3]2+. Photolysis of an aqueous solution of [(TMT)(p-cymene)Ru]2+ gives primarily [(TMT)Ru(H2O)3]2+. A procedure is described for the reversible loading of 1 onto γ-alumina, which in turn was characterized by 13C CP-MAS NMR spectroscopy.

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