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Structural and electrochemical comparison of trinuclear ruthenium oxo clusters [Ru 3 (OAc) 6 O( L ) 3 ] + and [Ru 3 (OAc) 6 O( L ) 2 (CO)] ( L = imidazole, benzimidazole, and 4‐phenylpyridine)
Author(s) -
Derstine Brandon,
Chamberlain Carmen,
Glover Morgan,
Porter Lindsey,
Eckermann Amanda
Publication year - 2018
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229618013451
Subject(s) - imidazole , chemistry , ruthenium , acetonitrile , medicinal chemistry , hexafluorophosphate , hexa , electrochemistry , crystal structure , methanol , benzimidazole , stereochemistry , crystallography , catalysis , ionic liquid , organic chemistry , electrode
The triruthenium oxo clusters [Ru 3 (OAc) 6 O( L ) 3 ] + and [Ru 3 (OAc) 6 O( L ) 2 (CO)] possess unique electronic characteristics that vary based on the ligands L . Here we report an investigation of the structural, electrochemical, and optical properties of clusters with imidazole, benzimidazole, and 4‐phenylpyridine ligands. The complexes [Ru 3 (OAc) 6 O( L ) 3 ] + [ 1 + : L = imidazole (im); 2 + : L = benzimidazole (benzim); 3 + : L = 4‐phenylpyridine (4PP)] and [Ru 3 (OAc) 6 O( L ) 2 (CO)] ( 1‐CO and 3‐CO ) were synthesized by reaction of either [Ru 3 (OAc) 6 O(MeOH) 3 ] + or [Ru 3 (OAc) 6 O(MeOH) 2 (CO)], respectively, with the corresponding heterocycle. We further discovered that [3]OAc could be reduced to the mixed‐valence neutral state 3 by refluxing the complex under nitrogen in methanol. Single‐crystal X‐ray structure analysis of hexa‐μ 2 ‐acetato‐μ 3 ‐oxido‐tris(1 H ‐imidazole)triruthenium hexafluorophosphate acetonitrile hemisolvate, [Ru 3 (C 2 H 3 O 2 ) 6 O(C 3 H 4 N 2 ) 3 ]PF 6 ·0.5CH 3 CN, [1]PF 6 , hexa‐μ 2 ‐acetato‐carbonylbis(1 H ‐imidazole)‐μ 3 ‐oxido‐triruthenium methanol monosolvate, [Ru 3 (C 2 H 3 O 2 ) 6 O(C 3 H 4 N 2 )(CO)]·CH 3 OH, 1‐CO , hexa‐μ 2 ‐acetato‐μ 3 ‐oxido‐tris(4‐phenylpyridine)triruthenium pentahydrate, [Ru 3 (C 2 H 3 O 2 ) 6 O(C 11 H 9 N) 3 ]·5H 2 O, 3 , and hexa‐μ 2 ‐acetato‐carbonyl‐μ 3 ‐oxido‐bis(4‐phenylpyridine)triruthenium methanol monosolvate, [Ru 3 (C 2 H 3 O 2 ) 6 O(C 11 H 9 N) 2 (CO)]·CH 3 OH, 3‐CO , show the expected triruthenium μ 3 ‐oxo core and N ‐coordination of the ligands. Cyclic voltammetry revealed quasi‐reversible and irreversible redox couples in [1]PF 6 , 1‐CO , and [2]PF 6 , while [3]PF 6 and 3‐CO exhibit reversible redox couples. The optical properties of these richly colored species were investigated using UV–Vis spectroscopy.