Parallel disulfido bridges in bi- and poly-nuclear transition metal compounds: Bonding flexibility induced by redox chemistry (Articolo in rivista)

Type

• Articolo in rivista (Classe)
• Prodotto della ricerca (Classe)

Label

• Parallel disulfido bridges in bi- and poly-nuclear transition metal compounds: Bonding flexibility induced by redox chemistry (Articolo in rivista) (literal)

Anno

• 2008-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1016/j.ica.2008.03.060 (literal)

Alternative label

• Mealli, Carlo; Ienco, Andrea; Messaoudi, Abdelatif; Poduska, Anne; Hoffmann, Roald (2008)
  Parallel disulfido bridges in bi- and poly-nuclear transition metal compounds: Bonding flexibility induced by redox chemistry
  in Inorganica Chimica Acta (Testo stamp.); Elsevier Science SA, Lausanne (Svizzera)
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• Mealli, Carlo; Ienco, Andrea; Messaoudi, Abdelatif; Poduska, Anne; Hoffmann, Roald (literal)

Pagina inizio

• 3631 (literal)

Pagina fine

• 3637 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 361 (literal)

Rivista

• Inorganica Chimica Acta (Rivista)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• CNR, ICCOM, Ist Chim Composti Organomet, I-50019 Florence, Italy Cornell Univ, Baker Lab, Dept Chem & Chem Biol, Ithaca, NY 14853 USA (literal)

Titolo

• Parallel disulfido bridges in bi- and poly-nuclear transition metal compounds: Bonding flexibility induced by redox chemistry (literal)

Abstract

• We recently studied an elongated S(4)(2-) rectangle bridging transition metals such as Ir, Rh, Cu, or Fe and found that its formation is related to the oxidation of parallel S(2)(2-) molecules. The removal of two electrons can occur either externally or by an internal metal-ligand redox process that implies depopulation of the high-lying S(4) sigma(*) MO and population of a lower metal level. Thus, the interaction may be described as metal back-donation. However, sufficiently electropositive metals can more easily reach higher oxidation states and this reverses the direction of the two-electron interaction. In such a case, the system may be viewed as formed by two uncoupled disulfides donating an additional electron pair to the metals. In this paper, we analyze the aspects of the 2S(2)(2-)/S(4)(2-) dichotomy through DFT calculations and qualitative MO analysis of the known bimetallic MS(4)M cores having either triple-decker (TD) or chair-type structures. We correlate the extent of the disulfide coupling with the nature (electronegativity) of the terminal metal fragments (the metals range from Group IV to X) beside their electron configuration. We find that the formation of an S(4)(2-) unit is favored by metals which cannot stabilize high oxidation states (e. g. Fe(IV) or Cu(III)), whereas the two S(2)(2-) units remain substantially uncoupled with early transition metal in high oxidation states (e.g. Ti(IV)). (literal)

Editore

• Elsevier Science SA (Editore)

Prodotto di

• Studi modellistici per l’attivazione dell’idrogeno molecolare da parte di sistemi metallici anche con finalità biomimetiche (PM.P07.007.001) (Modulo)
• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)

Autore CNR

• ABDELATIF MESSAOUDI (Unità di personale esterno)
• ANDREA IENCO (Persona)
• CARLO MEALLI (Persona)

Incoming links:

Prodotto

• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)
• Studi modellistici per l’attivazione dell’idrogeno molecolare da parte di sistemi metallici anche con finalità biomimetiche (PM.P07.007.001) (Modulo)

Autore CNR di

• ANDREA IENCO (Persona)
• CARLO MEALLI (Persona)
• ABDELATIF MESSAOUDI (Unità di personale esterno)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• Inorganica Chimica Acta (Rivista)

Editore di

• Elsevier Science SA (Editore)