Reactivity of Novel N,N'-Diphosphino-Silanediamine-Based Rhodium(I) Derivatives (Articolo in rivista)

Type
Label
  • Reactivity of Novel N,N'-Diphosphino-Silanediamine-Based Rhodium(I) Derivatives (Articolo in rivista) (literal)
Anno
  • 2011-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ic2004408 (literal)
Alternative label
  • Passarelli Vincenzo ; Benetollo Franco (2011)
    Reactivity of Novel N,N'-Diphosphino-Silanediamine-Based Rhodium(I) Derivatives
    in Inorganic chemistry
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Passarelli Vincenzo ; Benetollo Franco (literal)
Pagina inizio
  • 9958 (literal)
Pagina fine
  • 9967 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://pubs.acs.org/doi/abs/10.1021/ic2004408 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 50 (literal)
Rivista
Note
  • Scopu (literal)
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1 : Centro Universitario de la Defensa, Ctra. Huesca s/n, ES-50090 Zaragoza, Espana 2 : Istituto di Chimica Inorganica e delle Superfici (ICIS), Consiglio Nazionale delle Ricerche, Corso Stati Uniti 4, I-35127 Padova, Italia (literal)
Titolo
  • Reactivity of Novel N,N'-Diphosphino-Silanediamine-Based Rhodium(I) Derivatives (literal)
Abstract
  • The coordination abilities of the novel N,N2-diphosphino-silanediamine ligand of formula SiMe2(NtolPPh2)2 (SiNP, 1) have been investigated toward rhodium, and the derivatives [RhCl(SiNP)]2 (2), [Rh(SiNP)(COD)][BF4] (3), and Rh(acac)(SiNP) (4) have been synthesized.The stability of the dinuclear frame of [RhCl(SiNP)]2 (2) toward incoming nucleophiles has been shown to be dependent on their À-acceptor ability.Indeed, the mononuclear complexes RhCl(SiNP)(L) (L = CO, 5; CNtBu, 6) have been isolated purely and quantitatively upon reaction of 2 with CO and CNtBu, respectively.Otherwise, PPh3 and RhCl(SiNP) equilibrate with Rh(Cl)(SiNP)(PPh3) (7). Carbon electrophiles such as MeI and 3-chloro-1-proprene afforded the oxidation of rhodium(I) to rhodium(III) and the formation of RhCl2(·3-C3H5)(SiNP) (8) and Rh(Me)(I)(SiNP)(acac) (10), respectively. The methyl derivative 10 is thermally stable and does not react either with CO or with CNtBu even in excess. Otherwise, RhCl2(·3-C3H5)(SiNP) (8) is thermally stable but reacts with CO, affording 3-chloro-1-proprene and RhCl(SiNP)(CO) (5). Finally, upon reaction of Rh(acac)(SiNP) (4) and 3-chloro-1-proprene, RhCl(acac)(·1-C3H5)(SiNP) (9a) and [Rh(acac)(·3-C3H5)(SiNP)]Cl (9b) could be detected at 233 K. At higher temperatures, 9a and 9b smoothly decompose, affording the dinuclear derivative [RhCl(SiNP)]2 (2) and the CC coupling product 3-allylpentane-2,4-dione. (literal)
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