Electronic aspects of the phosphine-oxide -> phosphinous acid tautomerism and the assisting role of transition metal centers (Articolo in rivista)

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Label
  • Electronic aspects of the phosphine-oxide -> phosphinous acid tautomerism and the assisting role of transition metal centers (Articolo in rivista) (literal)
Anno
  • 2014-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1016/j.jorganchem.2013.10.043 (literal)
Alternative label
  • Manca, Gabriele; Caporali, Maria; Ienco, Andrea; Peruzzini, Maurizio; Mealli, Carlo (2014)
    Electronic aspects of the phosphine-oxide -> phosphinous acid tautomerism and the assisting role of transition metal centers
    in Journal of organometallic chemistry (Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Manca, Gabriele; Caporali, Maria; Ienco, Andrea; Peruzzini, Maurizio; Mealli, Carlo (literal)
Pagina inizio
  • 177 (literal)
Pagina fine
  • 185 (literal)
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  • http://www.scopus.com/inward/record.url?eid=2-s2.0-84899458702&partnerID=q2rCbXpz (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 760 (literal)
Rivista
Note
  • Scopu (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Consiglio Nazionale Delle Ricerche, Istituto di Chimica Dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy (literal)
Titolo
  • Electronic aspects of the phosphine-oxide -> phosphinous acid tautomerism and the assisting role of transition metal centers (literal)
Abstract
  • The H3P(O) / H2P(OH) tautomerism is addressed by experimental and DFT approaches. The process, disfavored for the free molecule, is easier over metal fragments of the type {CpRuIIL2}n (L ¼ uncharged or anionic phosphine ligand), with an energy barrier reduced to one fourth. The free H3P(O) molecule is a very weak acid and hardly a proton migrates intra-molecularly towards the oxo atom, as expected for classic acid-base reactions. Rather, some electron density of the highly covalent PeH bond remains anchored to the H atom at least up to the TS with the barrier originated from the electronic repulsion with the approached O lone pair. Beyond TS, the H atom transforms into a proton after having released its electron portion at the P atom (lone pair). The calculations show the experimentally undetected intermediate [CpRu(PR3)2(H)(H2PO)]n, at which the metal has induced a PeH oxidative addition. Consistent behaviors are found for all the molecules Hn(OH)3?nP(O) (n ¼ 3, 2, 1), whereas some anomalies have been experimentally observed with the anionic TPPMS coligands [TPPMS ¼ PPh2(m-C6H4SO3)?], used to favor the chemistry in water. In particular: i) the reaction with H3P(O) indicates that the product [CpRu(TPPMS)2{H2P(OH)}]? exists in two isomeric forms; ii) the tautomerization of H(OH)2P(O) is uniquely inhibited. Ad-hoc DFT calculations indicate that the features are attributable to the strong Hbonding networks between the sulphonate substituent and OH group(s) and water as well. (literal)
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