Charged, but Found "Not Guilty": Innocence of the Suspect Bridging Ligands [RO(O)CNNC(O)OR](2-) = L2- in [(acac)(2)Ru(mu-L)Ru(acac)(2)](n), n = +,0,-,2-
Result description
Neutral diastereoisomeric diruthenium(III) complexes, meso- and rae-[(acac)(2)Ru(mu-adc-OR)Ru(acac)(2)) (acac(-) = 2,4-pentanedionato and adc-OR2- = dialkylazodicarboxylato = [RO(O)CNNC(O)OR](2-), R = tert-butyl or isopropyl), were obtained from electrontransfer reactions between Ru(acac)(2)(CH3CN)(2) and azodicarboxylic acid diallcyl esters (adc-OR). The mew,P isomer 3 with R = isopropyl was structurally characterized, revealing two deprotonated and N-N coupled carbamate functions in a reduced dianionic bridge with d(N-N) = 1.440(5) angstrom. A rather short distance of 4.764 angstrom has been determined between the two oxidized, antiferromagnetically coupled Ru-III centers. The rac isomer 4 with R = isopropyl exhibited stronger antiferromagnetic coupling. While the oxidation of the neutral compounds was fully reversible only for 3 and 4, two well-separated (10(8) < K-c < 10(10)) reversible one-electron reduction steps produced monoanionic intermediates 1(-)-4(-) with intense (epsilon
Keywords
DINUCLEAR RUTHENIUM COMPLEXESMOLECULAR-ORBITAL METHODSANION-RADICAL COMPLEXES
The result's identifiers
Result code in IS VaVaI
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
Charged, but Found "Not Guilty": Innocence of the Suspect Bridging Ligands [RO(O)CNNC(O)OR](2-) = L2- in [(acac)(2)Ru(mu-L)Ru(acac)(2)](n), n = +,0,-,2-
Original language description
Neutral diastereoisomeric diruthenium(III) complexes, meso- and rae-[(acac)(2)Ru(mu-adc-OR)Ru(acac)(2)) (acac(-) = 2,4-pentanedionato and adc-OR2- = dialkylazodicarboxylato = [RO(O)CNNC(O)OR](2-), R = tert-butyl or isopropyl), were obtained from electrontransfer reactions between Ru(acac)(2)(CH3CN)(2) and azodicarboxylic acid diallcyl esters (adc-OR). The mew,P isomer 3 with R = isopropyl was structurally characterized, revealing two deprotonated and N-N coupled carbamate functions in a reduced dianionic bridge with d(N-N) = 1.440(5) angstrom. A rather short distance of 4.764 angstrom has been determined between the two oxidized, antiferromagnetically coupled Ru-III centers. The rac isomer 4 with R = isopropyl exhibited stronger antiferromagnetic coupling. While the oxidation of the neutral compounds was fully reversible only for 3 and 4, two well-separated (10(8) < K-c < 10(10)) reversible one-electron reduction steps produced monoanionic intermediates 1(-)-4(-) with intense (epsilon
Czech name
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Czech description
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Classification
Type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2012
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
51
Issue of the periodical within the volume
17
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
9273-9281
UT code for WoS article
000308258700023
EID of the result in the Scopus database
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Basic information
Result type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP
CF - Physical chemistry and theoretical chemistry
Year of implementation
2012