Dihydrogen Bonding in Complex (PP3)RuH(eta1-BH4) Featuring Two Proton-Accepting Hydride Sites: Experimental and Theoretical Studies (Articolo in rivista)

Type

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

Label

• Dihydrogen Bonding in Complex (PP3)RuH(eta1-BH4) Featuring Two Proton-Accepting Hydride Sites: Experimental and Theoretical Studies (Articolo in rivista) (literal)

Anno

• 2014-01-01T00:00:00+01:00 (literal)

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

• 10.1021/ic4026206 (literal)

Alternative label

• Belkova, Natalia; Bakhmutova, Ekaterina; Gutsul, Evgenii; Bahkmutov, Vladimir; Golub, Igor; Filippov, Oleg; Epstein, Lina; Peruzzini, Maurizio; Rossin, Andrea; Zanobini, Fabrizio; Shubina, Elena (2014)
  Dihydrogen Bonding in Complex (PP3)RuH(eta1-BH4) Featuring Two Proton-Accepting Hydride Sites: Experimental and Theoretical Studies
  in Inorganic chemistry; ACS, American chemical society, Washington, DC (Stati Uniti d'America)
  (literal)

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

• Belkova, Natalia; Bakhmutova, Ekaterina; Gutsul, Evgenii; Bahkmutov, Vladimir; Golub, Igor; Filippov, Oleg; Epstein, Lina; Peruzzini, Maurizio; Rossin, Andrea; Zanobini, Fabrizio; Shubina, Elena (literal)

Pagina inizio

• 1080 (literal)

Pagina fine

• 1090 (literal)

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

• 53 (literal)

Rivista

• Inorganic chemistry (Rivista)

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

• 11 (literal)

Note

• Scopus (literal)
• ISI Web of Science (WOS) (literal)

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

• A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 119991 Moscow, Russia Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), via Madonna del Piano 10, 50019 Sesto Fiorentino (Florence), Italy (literal)

Titolo

• Dihydrogen Bonding in Complex (PP3)RuH(eta1-BH4) Featuring Two Proton-Accepting Hydride Sites: Experimental and Theoretical Studies (literal)

Abstract

• Combining variable-temperature infrared and NMR spectroscopic studies with quantum-chemical calculations (density functional theory (DFT) and natural bond orbital) allowed us to address the problem of competition between MH (M = transition metal) and BH hydrogens as proton-accepting sites in dihydrogen bond (DHB) and to unravel the mechanism of proton transfer to complex (PP3)RuH(?1-BH4) (1, PP3 = ?4-P(CH2CH2PPh2)3). Interaction of complex 1 with CH3OH, fluorinated alcohols of variable acid strength [CH2FCH2OH, CF3CH2OH, (CF3)2CHOH (HFIP), (CF3)3COH], and CF3COOH leads to the medium strength DHB complexes involving BH bonds (3-5 kcal/mol), whereas DHB complexes with RuH were not observed experimentally. The two proton-transfer pathways were considered in DFT/M06 calculations. The first one goes via more favorable bifurcate complexes to BHterm and high activation barriers (38.2 and 28.4 kcal/mol in case of HFIP) and leads directly to the thermodynamic product [(PP3)RuHeq(H2)]+[OR]-. The second pathway starts from the less-favorable complex with RuH ligand but shows a lower activation barrier (23.5 kcal/mol for HFIP) and eventually leads to the final product via the isomerization of intermediate [(PP3)RuHax(H2)]+[OR]-. The B-Hbr bond breaking is the common key step of all pathways investigated. (literal)

Editore

• ACS, American chemical society (Editore)

Prodotto di

• Nuovi materiali per 'storage' e produzione di idrogeno (PM.P03.005.001) (Modulo)
• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)

Autore CNR

• ANDREA ROSSIN (Persona)
• MAURIZIO PERUZZINI (Unità di personale interno)
• FABRIZIO ZANOBINI (Unità di personale esterno)

Incoming links:

Prodotto

• Istituto di chimica dei composti organo metallici (ICCOM) (Istituto)
• Nuovi materiali per 'storage' e produzione di idrogeno (PM.P03.005.001) (Modulo)

Autore CNR di

• MAURIZIO PERUZZINI (Unità di personale interno)
• FABRIZIO ZANOBINI (Unità di personale esterno)
• ANDREA ROSSIN (Persona)

Editore di

• ACS, American chemical society (Editore)

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

• Inorganic chemistry (Rivista)