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

Journal Article · Wed Nov 22 04:00:00 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), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:24; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360104* -- Metals & Alloys-- Physical Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
54 ENVIRONMENTAL SCIENCES
540120 -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (1990-)
ATMOSPHERIC CHEMISTRY
CHEMISTRY
COMBUSTION PRODUCTS
DATA
DATA ANALYSIS
DIMERS
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PLATINUM METALS
RUTHENIUM
SYNTHESIS
THIOPHENE
TRANSITION ELEMENTS