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dc.contributor.author
Khan, Farheen Fatima
dc.contributor.author
Mondal, Saikat
dc.contributor.author
Chandra, Shubhadeep
dc.contributor.author
Neuman, Nicolás Ignacio
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dc.contributor.author
Sarkar, Biprajit
dc.contributor.author
Lahiri, Goutam Kumar
dc.date.available
2021-07-11T20:07:29Z
dc.date.issued
2021-01
dc.identifier.citation
Khan, Farheen Fatima; Mondal, Saikat; Chandra, Shubhadeep; Neuman, Nicolás Ignacio; Sarkar, Biprajit; et al.; On the non-innocence and reactive: Versus non-reactive nature of α-diketones in a set of diruthenium frameworks; Royal Society of Chemistry; Dalton Transactions; 50; 3; 1-2021; 1106-1118
dc.identifier.issn
1477-9226
dc.identifier.uri
http://hdl.handle.net/11336/135784
dc.description.abstract
α-Diketones are an important class of building blocks employed in many organic synthetic reactions. However, their coordination chemistry has rarely been explored. In light of this, our earlier report on [(acac)2RuII(μ-2,2′-pyridil)RuII(acac)2] (acac = acetylacetonate) showcased the sensitivity of a diketone fragment towards oxidative C-C cleavage. Following the lead, the synthesis of similar but stable diketo fragments containing diruthenium compounds was attempted. Three diruthenium compounds with the bridge 1,2-bis(2-hydroxyphenyl)ethane-1,2-dione (L) were prepared: diastereomeric [(acac)2RuIII(μ-L2-)RuIII(acac)2], 1a(rac)/1b(meso), [(bpy)2RuII(μ-L2-)RuII(bpy)2](ClO4)2, [2](ClO4)2 and [(pap)2RuII(μ-L2-)RuII(pap)2](ClO4)2, [3](ClO4)2 with ancillary ligands of different donating/accepting characteristics. The metal is stabilised in different oxidation states in these complexes: Ru(iii) is preferred in 1a/1b when σ-donating acac is used as the co-ligand whereas electron rich Ru(ii) is preferred in [2](ClO4)2 and [3](ClO4)2 when co-ligands of moderate to strong π-Accepting properties are employed. The oxidative chemistry of these systems is of particular interest with respect to the participation of varying bridging-ligands which contain phenoxide groups. On the other hand, the reduction processes primarily resulting from the metal or the ancillary ligands are noteworthy as the normally reducible 1,2-diketo-group remains unreduced. These results have been rationalised and outlined from thorough experimental and theoretical investigations. The results presented here shed light on the stability of metal coordinated α-diketones as a function of their substituents.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
RUTHENIUM
dc.subject
NON-INNOCENT
dc.subject.classification
Química Inorgánica y Nuclear
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
On the non-innocence and reactive: Versus non-reactive nature of α-diketones in a set of diruthenium frameworks
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2021-07-01T17:33:12Z
dc.journal.volume
50
dc.journal.number
3
dc.journal.pagination
1106-1118
dc.journal.pais
Reino Unido
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dc.journal.ciudad
Cambridge
dc.description.fil
Fil: Khan, Farheen Fatima. Indian Institute Of Technology, Bombay; India
dc.description.fil
Fil: Mondal, Saikat. Indian Institute Of Technology, Bombay; India
dc.description.fil
Fil: Chandra, Shubhadeep. Universität Stuttgart; Alemania
dc.description.fil
Fil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
dc.description.fil
Fil: Sarkar, Biprajit. Universität Stuttgart; Alemania
dc.description.fil
Fil: Lahiri, Goutam Kumar. Indian Institute Of Technology, Bombay; India
dc.journal.title
Dalton Transactions
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/d0dt03400b
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