Nucleophilic Addition of Phosphines to Rhenium Allenylidenes. Unprecedented Double P-H Bond Activation to GIve an h1-P-phospha-1-butadienyl Ligand (Articolo in rivista)

Type
Label
  • Nucleophilic Addition of Phosphines to Rhenium Allenylidenes. Unprecedented Double P-H Bond Activation to GIve an h1-P-phospha-1-butadienyl Ligand (Articolo in rivista) (literal)
Anno
  • 2003-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1039/B303216G (literal)
Alternative label
  • Peruzzini, Maurizio; Barbaro, Pierluigi; Bertolasi, Valerio; Bianchini, Claudio, De los Rios, Isaac; Mantovani Nicoletta; Marvelli, Lorenza; Rossi, Roberto (2003)
    Nucleophilic Addition of Phosphines to Rhenium Allenylidenes. Unprecedented Double P-H Bond Activation to GIve an h1-P-phospha-1-butadienyl Ligand
    in Dalton transactions (2003. Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Peruzzini, Maurizio; Barbaro, Pierluigi; Bertolasi, Valerio; Bianchini, Claudio, De los Rios, Isaac; Mantovani Nicoletta; Marvelli, Lorenza; Rossi, Roberto (literal)
Pagina inizio
  • 4121 (literal)
Pagina fine
  • 4131 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#altreInformazioni
  • L'articolo pubblicato su una rivista della Royal Society of Chemitry a buon indice di impatto (IF > 3) descrive la reattività di fosfine primarie, secondarie e terziarie con allenilideni di renio e chiarisce in modo univoco il meccanismo della reazione. L'addizione di legami P-H sulla catena allenilidenica conduce alla formazione di notevoli prodotti (fosfabutadieni) in cui un atomo di fosforo è incorporato nella catena C3. (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#descrizioneSinteticaDelProdotto
  • Tertiary phosphines PR3 react with the rhenium allenylidene [(triphos)(CO)2Re(C=C=CPh2)]OTf (1) yielding kinetic g-phosphonioalkynyl complexes [(triphos)(CO)2Re{CºCCPh2(PR3)}]Otf. Increasing the temperature converts the g-phosphonioalkynyl compounds into the thermodynamically stable a-phosphonioallenyl derivatives [(triphos)(CO)2Re{C(PR3)=C=CPh2}]OTf. The reactions of 1 with secondary, PHPh2, and primary, PH2CH2Fc (Fc = ferrocenyl), phosphines have been found to proceed with a similar mechanism, followed by thermally driven single or double P-H bond cleavage. As a result, a-phosphoniobutadienyl derivatives [(triphos)(CO)2Re{C(=PR2)CH=CPh2}]OTf and h1-P-phospha-1-butadienyl complex [(triphos)(CO)2Re{P(R)=CHCH=CPh2}]OTf are, respectively, obtained upon heating (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via J. Nardi 39, 50132 Firenze, Italy. Centro di Strutturistica Diffrattometrica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy. Departamiento de Ciencia de los Materiales e Ing. Met. y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, Puerto Real 11510, Spain. Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy. (literal)
Titolo
  • Nucleophilic Addition of Phosphines to Rhenium Allenylidenes. Unprecedented Double P-H Bond Activation to GIve an h1-P-phospha-1-butadienyl Ligand (literal)
Abstract
  • Tertiary phosphines PMe3-xPhx (x = 0 – 2) react with the rhenium allenylidene [(triphos)(CO)2Re(C=C=CPh2)]OTf (1) yielding kinetic g-phosphonioalkynyl complexes [(triphos)(CO)2Re{CºCCPh2(PMe3-xPhx)}]OTf [x = 0, (2); 1, (4); 2 (7)]. Increasing the temperature converts the g-phosphonioalkynyl compounds into the thermodynamically stable a-phosphonioallenyl derivatives [(triphos)(CO)2Re{C(PMe3-xPhx)=C=CPh2}]OTf [x = 0, (3); 1, (5); 2 (6)]. The reactions of 1 with secondary, PHPh2, and primary, PH2CH2Fc (Fc = ferrocenyl), phosphines have been found to proceed with a similar mechanism, followed by single or double P-H bond cleavage. The g-phosphonioalkynyl [(triphos)(CO)2Re{CºCCPh2(PHPh2)}]OTf (9) and the a-phosphonioallenyl [(triphos)(CO)2Re{C(PHPh2)=C=CPh2}]OTf (10) have been intercepted by in situ NMR spectroscopy. On increasing the temperature, 10 undergoes a selective 1,3-P,C-H shift to give the a-phosphoniobutadienyl derivative [(triphos)(CO)2Re{C(=PPh2)CH=CPh2}]OTf (8). With the primary phosphine PH2CH2Fc, the a-phosphoniobutadienyl complex [(triphos)(CO)2Re{C(=PHFc)CH=CPh2}]OTf (11) was initially formed which transforms into the h1-P-phosphabutadienyl complex [(triphos)(CO)2Re{P(CH2Fc)=CHCH=CPh2}]OTf (12) upon heating at 50 °C following a second P-H bond activation and C,P-metal bonding isomerisation. Compound 1/BPh4 has been authenticated by an X-ray diffraction analysis. The structure of this complex shows the metal center to be surrounded by a fac triphos ligand, by two mutually cis carbonyl groups and by the allenylidene ligand in a slightly distorted octahedral geometry. (literal)
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