The platinum(I) dinuclear carbonyl [Pt-2(mu -PBu2t)(2)((PBu2H)-H-t)(CO)] (1) reacts with organic isonitriles RNC (R = p-tolyl, Bu-t, PhCH2), yielding the mono- and disubstituted derivatives [Pt-2(mu -PBu2t)(2)((PBu2H)-H-t)(CNR)] (2, R = p-tolyl; 3, R = Bu-t; 4, R = PhCH2) and [Pt(mu -PBu2t)(CNR)](2) (5, R = p-tolyl; 6, R = Bu-t; 7, R = PhCH2). Only with the aromatic isonitrile does the reaction proceed through two further well-separated steps, giving [Pt-2(mu -PBu2t){mu,eta (2)-P(Bu-2(t))C(=NAr)}(CNAr)(2)] (8) and [Pt{mu,eta (2)-P(Bu-2(t))C(=NAr)}(CNAr)](2) (9). These arise from the unprecedented reversible isonitrile insertion into the M-P bonds of the phosphido-bridges. When 8 or 9 are reacted with CF3SO3H, the cyclic carbenes [Pt-2(mu -PBu2t){mu,eta (2)-P(Bu-2(t))C(NHAr)}(CNAr)(2)]CF3SO3 (10) and [Pt{mu,eta (2)-P(Bu-2(t))C(NHAr)}(CNAr)](2) (CF3SO3)(2) (11) are respectively formed. The crystal and molecular structures of complexes 8 and 11 were solved by X-ray diffraction.

The first examples of isonitrile insertion into a phosphido bridge and the crystal and molecular structures of [Pt-2(mu-PBu2t){mu,eta(2)-P(Bu-2(t))C(=NAr)}(CNAr)(2)] and [Pt{mu,eta(2)-P(Bu-2(t))C (NHAr)}(CNAr)](2)(CF3SO3)(2) (Ar = p-tolyl) / S. Cristofani, P. Leoni, M. Pasquali, F. Eisentraeger, A. Albinati. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 19:22(2000 Oct 30), pp. 4589-4595.

The first examples of isonitrile insertion into a phosphido bridge and the crystal and molecular structures of [Pt-2(mu-PBu2t){mu,eta(2)-P(Bu-2(t))C(=NAr)}(CNAr)(2)] and [Pt{mu,eta(2)-P(Bu-2(t))C (NHAr)}(CNAr)](2)(CF3SO3)(2) (Ar = p-tolyl)

A. Albinati
Ultimo
2000

Abstract

The platinum(I) dinuclear carbonyl [Pt-2(mu -PBu2t)(2)((PBu2H)-H-t)(CO)] (1) reacts with organic isonitriles RNC (R = p-tolyl, Bu-t, PhCH2), yielding the mono- and disubstituted derivatives [Pt-2(mu -PBu2t)(2)((PBu2H)-H-t)(CNR)] (2, R = p-tolyl; 3, R = Bu-t; 4, R = PhCH2) and [Pt(mu -PBu2t)(CNR)](2) (5, R = p-tolyl; 6, R = Bu-t; 7, R = PhCH2). Only with the aromatic isonitrile does the reaction proceed through two further well-separated steps, giving [Pt-2(mu -PBu2t){mu,eta (2)-P(Bu-2(t))C(=NAr)}(CNAr)(2)] (8) and [Pt{mu,eta (2)-P(Bu-2(t))C(=NAr)}(CNAr)](2) (9). These arise from the unprecedented reversible isonitrile insertion into the M-P bonds of the phosphido-bridges. When 8 or 9 are reacted with CF3SO3H, the cyclic carbenes [Pt-2(mu -PBu2t){mu,eta (2)-P(Bu-2(t))C(NHAr)}(CNAr)(2)]CF3SO3 (10) and [Pt{mu,eta (2)-P(Bu-2(t))C(NHAr)}(CNAr)](2) (CF3SO3)(2) (11) are respectively formed. The crystal and molecular structures of complexes 8 and 11 were solved by X-ray diffraction.
X-ray structure; 2,6-dimethylphenyl isocyanide; trihydride complexes; reactivity; ligands; bond; platinum; palladium; methylplatinum(II); derivatives
Settore CHIM/03 - Chimica Generale e Inorganica
Article (author)
File in questo prodotto:
File Dimensione Formato  
om000461t.pdf

accesso riservato

Tipologia: Publisher's version/PDF
Dimensione 105.78 kB
Formato Adobe PDF
105.78 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/256881
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 16
  • ???jsp.display-item.citation.isi??? 15
social impact