Unusual ligand design: A platinum(II) mediated [2+2] photocycloaddition followed by a nickel(II) induced methoxyactivation (Articolo in rivista)

Type
Label
  • Unusual ligand design: A platinum(II) mediated [2+2] photocycloaddition followed by a nickel(II) induced methoxyactivation (Articolo in rivista) (literal)
Anno
  • 2010-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1016/j.ica.2009.03.009 (literal)
Alternative label
  • Fessler, Markus; Czermak, Georg; Eller, Sylvia; Trettenbrein, Barbara; Haringer, Stephan; Oberhauser, Werner; Brüggeller, Peter (2010)
    Unusual ligand design: A platinum(II) mediated [2+2] photocycloaddition followed by a nickel(II) induced methoxyactivation
    in Inorganica Chimica Acta (Testo stamp.)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Fessler, Markus; Czermak, Georg; Eller, Sylvia; Trettenbrein, Barbara; Haringer, Stephan; Oberhauser, Werner; Brüggeller, Peter (literal)
Pagina inizio
  • 2001 (literal)
Pagina fine
  • 2008 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 363 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • ICCOM-CNR Institut fuer Allgemeine, Anorganische und Theoretische Chemie der Universitaet Innsbruck, Innrain 52a, 6020 Innsbruck, Austria (literal)
Titolo
  • Unusual ligand design: A platinum(II) mediated [2+2] photocycloaddition followed by a nickel(II) induced methoxyactivation (literal)
Abstract
  • The novel dimer of the composition [Pt2Cl4(l-(jP1:jP2-o-MeO-trans-dppen))2] (1) (o-MeO-transdppen = 1,2-(bis(o-methoxyphenyl)phosphanyl)ethylene) has been prepared and characterized by a single crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry and elemental analysis. This latter compound undergoes a [2+2] photocycloaddition reaction yielding the tetraphosphane all-trans- 1,2,3,4-tetrakis(di(o-methoxyphenyl)phosphanyl)cyclobutane (o-MeO-dppcb). The X-ray structure of the dimeric Ni(II) complex that contains the latter ligand, of the formula [Ni2Cl4(l-(jP1:jP2:jP3:jP4-o- MeO-dppcb))] (2) reveals that the apical coordination sites of both square pyramidal Ni(II) coordination spheres are occupied by methoxy-oxygen atoms of the ligand. As a consequence, this dimeric Ni(II) complex 2 is prone to a thermally induced regio- and diastereoselective metal-assisted methoxy-group cleavage. The stepwise formed new mono- and bis-phenolate complexes [Ni2Cl3(l-(jO1,jP1: jP2:jP3:jP4-o-MeO-O-dppcb))] (3) and [Ni2Cl2(l-(jO1,jP1:jP2:jO2,jP3:jP4-o-MeO-O,O0-dppcb))] (4), respectively, contain the novel chiral tetraphosphane ligands all-trans-1,2,3-tris((di-o-methoxyphenyl) phosphano)-4-((o-methoxy-phenyl)(o-phenolate)phosphano)cyclobutane (o-MeO-O-dppcb) and all-trans-1,2-bis((di-o-methoxyphenyl)phosphano)-3,4-bis((o-methoxyphenyl) (o-phenolate)phosphano) cyclobutane (o-MeO-O,O0-dppcb). Compounds 3 and 4 have been synthesized independently and are also fully characterized by both single crystal X-ray structure analyses, NMR spectroscopy, mass spectrometry and elemental analyses. The conversion of 2 into 3 and then further into 4 has been followed by a variable-temperature 31P{1H} NMR experiment with compound 2 in DMF-d7, revealing that the cleavage of the second methoxy group is kinetically disfavoured. This is in agreement with the X-ray structure analysis of 3, indicating the lack of any methoxy-oxygen atom coordination that could easily induce a further methoxy-group cleavage. o-MeO-O-dppcb and o-MeO-O,O0-dppcb are rare P-stereogenic tetraphosphine ligands and contribute to the synthetic field of new j3-P,P,O-coordinating phosphanylphenolate ligands that are believed to be important for the SHOP process (SHOP, Shell Higher Olefin Process). (literal)
Prodotto di
Autore CNR
Insieme di parole chiave

Incoming links:


Prodotto
Autore CNR di
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi
Insieme di parole chiave di
data.CNR.it