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Extended Electronic Interactions in a Triangular μ‐Oxotriruthenium Acetate Cluster Containing Nitric Oxide
Author(s) -
Toma Henrique E.,
Alexiou Anamaria D. P.,
Dovidauskas Sergio
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200211)2002:11<3010::aid-ejic3010>3.0.co;2-l
Subject(s) - chemistry , unpaired electron , diamagnetism , electron paramagnetic resonance , cluster (spacecraft) , atomic orbital , crystallography , electrochemistry , pyridine , computational chemistry , inorganic chemistry , electron , molecule , nuclear magnetic resonance , medicinal chemistry , organic chemistry , physics , electrode , quantum mechanics , magnetic field , computer science , programming language
The binding of NO to the trinuclear cluster [Ru 3 O(CH 3 CO 2 ) 6 (py) 2 ] + (py = pyridine) leads to a stable, diamagnetic [Ru 3 O(CH 3 CO 2 ) 6 (py) 2 (NO)] + complex, displaying extended electronic interactions which arise from the coupling of the unpaired π* electron of NO and the unpaired electron in the π‐orbitals of the Ru 3 O unit. This complex has been isolated and its spectroscopic characterization (EPR, 1 H and 13 C NMR, IR, UV/Vis) and electrochemical/spectroelectrochemical properties are reported in this paper. The NO 0 character in the complex is supported by spectroscopic and electrochemical results, as well as by semi‐empirical theoretical calculations carried out for the complex. A remarkable point in this system is the dramatic changes in the Ru−NO electronic interactions accompanying the several successive redox states of the triangular Ru 3 O center. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)