(Tetramethylthiophene)ruthenium in dichloride dimer: A versatile synthetic intermediate in thiophene coordination chemistry

Journal Article · Wed Nov 22 00:00:00 EST 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00206a010· OSTI ID:7074498

Lockemeyer, J R; Rauchfuss, T B; Wilson, S R ^[1]; Rheingold, A L ^[2]

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1. Univ. of Illinois, Urbana (USA)
2. Univ. of Delaware, Newark (USA)

The thermal reaction of ((cymene)RuCl{sub 2}){sub 2} and tetramethylthiophene (TMT) gives ((TMT)RuCl{sub 2}){sub 2} (1). Treatment of 1 with silver salts in the presence of various ligands gives salts of ((TMT)RuL{sub 3}){sup 2+} where L{sub 3} = (H{sub 2}O){sub 3}, (CH{sub 3}CN){sub 3}, and TMT. A crystallographic study demonstrated that ((TMT){sub 2}Ru)(BF{sub 4}){sub 2} {times} 2CH{sub 3}NO{sub 2} adopts a sandwich structure with sulfur atoms sited cis on the pseudooctahedron. Cyclic voltammetry studies show that ((TMT){sub 2}Ru){sup 2+} undergoes 2 reversible one-electron reductions. Solutions of 1 and phosphine and amine donors react to give well-behaved monometallic derivatives of the type (TMT)RuCl{sub 2}L where L is PR{sub 3} and NH{sub 2}C{sub 6}H{sub 4}Me. For bulky L = PPh{sub 3} and P(C{sub 6}H{sub 4}Me){sub 3}, variable-temperature NMR studies demonstrate hindered rotation about the Ru-P and Ru{hor ellipsis} TMT axes. Treatment of 1 with (Me{sub 3}Si){sub 2}S gives the cluster ((TMT)RuCl){sub 3}S{sup +} whose PF{sub 6}{sup {minus}} salt was examined by X-ray crystallography. The cluster is comprised of 3 conjoined pseudooctahedral Ru centers bridged by 1 {mu}{sub 3}-S and 3 {mu}-Cl atoms.

• OSTI ID: 7074498
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 111:24; ISSN 0002-7863
• Country of Publication: United States
• Language: English

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36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
THIOPHENE
SYNTHESIS
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MEASURING INSTRUMENTS
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ORGANOMETALLIC COMPOUNDS
RUTHENIUM
CHEMISTRY
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ELEMENTS
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INFORMATION
METALS
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360104* - Metals & Alloys- Physical Properties
400201 - Chemical & Physicochemical Properties
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Atmospheric- Chemicals Monitoring & Transport- (1990-)