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1. Facile amido to pyridyl isomerization: pentaammineruthenium(II) walks the nicotinamide and isonicotinamide rings

Author

Chou, Mei H., Rong Chin Chang, and Chin-Tung Lin

Subjects
Isomerization -- Research, Cyclic compounds -- Research, Amides -- Research, Coordination compounds -- Research, Chemistry
Abstract

Evidence for the metastability of the Ru-carbon bond in ruthenium congeners of eta2-alkene, alkyne and arene and eta2-C-O acetone species, which results in the inability undergo a functional group to aromatic ring isomerization. The reduction of amido-bonded ruthenium(III) complexes of nicotinamide and isonicotinamide produce the ruthenium(II) complexes Ru(II)(NH3)5(HNC(O)-3-Py)1+ and Ru(II)(NH3)5(NHC(O)-4-py)1+. These complexes are subject to rapid intramolecular isomerization to the pyridyl bonded forms via aromatic ring-bonded intermediates.

Published
1992

2. Facile amino to pyridyl isomerization: pentaammineruthenium(II) walks the nicotinamide and isonicotinamide rings

Author

Rong Chin Chang, Norman Sutin, Mei H. Chou, Chin Tung Lin, Carol Creutz, Andrew Yeh, and Bruce S. Brunschwig

Subjects
Nicotinamide, medicine.drug_class, Stereochemistry, chemistry.chemical_element, Protonation, Carboxamide, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Intramolecular force, medicine, Osmium, Isonicotinamide, Physical and Theoretical Chemistry, Isomerization
Abstract

When amido-bonded ruthenium(III) complexes of both nicotinamide and isonicotinamide are reduced, the resulting ruthenium(II) complexes, Ru[sup II](NH[sub 3])[sub 5](NHC(O)-3-Py)[sup +] and Ru[sup II](NH[sub 3])[sub 5](NHC(O)-4-Py)[sup +], undergo rapid protonation, followed by intramolecular isomerization (k[sub 4-Py] = 9.6 s[sup [minus]1] at 25[degree]C) to the pyridyl-bonded forms. The authors believe these rearrangements proceed via [eta][sup 2]- arene-bonded intermediates in a walk of the aromatic ring as has been found for related osmium(II) complexes.

Published
1992

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