The platinum(I) dinuclear carbonyl [Pt2(μ-PtBu 2)2(PtBu2H)-(CO)] (4) reacts with carbon monoxide (80 atm) to give the dicarbonyl complex [Pt(μ-PtBu 2)(CO)]2 (9), which is thermally and air stable if protected from moisture. Wet solvents convert 9 into the known trinuclear hydride Pt3(μ-PtBu2)3(CO)2-(H) (10), which is also formed by treating 9 with molecular hydrogen (180 atm). The reaction of 4 or 9 with phosphanes [PR3 = PMe3, PPh 3, PCy3, PCy2H] results in the formation of the corresponding derivatives [Pt2(μ-PtBu2) 2(PtBu2H)(PR3)] [11, R = Me; 12, R = Ph; 13, R = Cy; 14, R3 = Cy2H], [Pt2(μ-PtBu 2)2(CO)(PR3)] [15, R = Me; 16, R = Ph; 17, R = Cy] or [Pt(μ-PtBu2)(PR3)]2 [18, R = Me; 19, R = Ph; 20, R = Cy] in good yields. Complex 19 is protonated at platinum by CF3SO3H yielding the hydride [Pt2(μ- PtBu2)2(H)(PPh3)2]-CF 3SO3 (21). The protonation of asymmetrically substituted 12 forms rapidly the kinetic hydride [(tBu2HP)Pt(μ-PtBu 2)2-Pt(H)(PPh3)]CF3SO3 (22a), which then isomerises slowly to the more stable isomer [(Ph 3P)Pt(μ-PtBu2)2Pt(H)(PtBu 2H)]-CF3SO3 (22b). Dicarbonyl 9 is instead protonated at the phosphorus atom of a bridging phosphide; the unstable product of this reaction can be intercepted by adding CO to give the monophosphido-bridged [Pt2(μ-PtBu2)(PtBu 2H)(CO)3]CF3-SO3 (24) as a mixture of two isomers. The X-ray crystal and molecular structures of 9, of a 2:1 mixture of 9 and 10, and of complexes 18, 19 and 21 are also reported.

Synthesis, structure and reactivity of bis(phosphido)-bridged dinuclear carbonyls of platinum(I) / A. Albinati, P. Leoni, F. Marchetti, L. Marchetti, M. Pasquali, S. Rizzato. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2009:26(2008), pp. 4092-4100. [10.1002/ejic.200800447]

Synthesis, structure and reactivity of bis(phosphido)-bridged dinuclear carbonyls of platinum(I)

A. Albinati
Primo
;
S. Rizzato
Ultimo
2008

Abstract

The platinum(I) dinuclear carbonyl [Pt2(μ-PtBu 2)2(PtBu2H)-(CO)] (4) reacts with carbon monoxide (80 atm) to give the dicarbonyl complex [Pt(μ-PtBu 2)(CO)]2 (9), which is thermally and air stable if protected from moisture. Wet solvents convert 9 into the known trinuclear hydride Pt3(μ-PtBu2)3(CO)2-(H) (10), which is also formed by treating 9 with molecular hydrogen (180 atm). The reaction of 4 or 9 with phosphanes [PR3 = PMe3, PPh 3, PCy3, PCy2H] results in the formation of the corresponding derivatives [Pt2(μ-PtBu2) 2(PtBu2H)(PR3)] [11, R = Me; 12, R = Ph; 13, R = Cy; 14, R3 = Cy2H], [Pt2(μ-PtBu 2)2(CO)(PR3)] [15, R = Me; 16, R = Ph; 17, R = Cy] or [Pt(μ-PtBu2)(PR3)]2 [18, R = Me; 19, R = Ph; 20, R = Cy] in good yields. Complex 19 is protonated at platinum by CF3SO3H yielding the hydride [Pt2(μ- PtBu2)2(H)(PPh3)2]-CF 3SO3 (21). The protonation of asymmetrically substituted 12 forms rapidly the kinetic hydride [(tBu2HP)Pt(μ-PtBu 2)2-Pt(H)(PPh3)]CF3SO3 (22a), which then isomerises slowly to the more stable isomer [(Ph 3P)Pt(μ-PtBu2)2Pt(H)(PtBu 2H)]-CF3SO3 (22b). Dicarbonyl 9 is instead protonated at the phosphorus atom of a bridging phosphide; the unstable product of this reaction can be intercepted by adding CO to give the monophosphido-bridged [Pt2(μ-PtBu2)(PtBu 2H)(CO)3]CF3-SO3 (24) as a mixture of two isomers. The X-ray crystal and molecular structures of 9, of a 2:1 mixture of 9 and 10, and of complexes 18, 19 and 21 are also reported.
Bridging ligands; Crystal structures; Dinuclear complexes; Phosphanes; Phosphido ligands; Platinum
Settore CHIM/03 - Chimica Generale e Inorganica
Article (author)
File in questo prodotto:
Non ci sono file associati a questo prodotto.
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/2434/60776
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 17
  • ???jsp.display-item.citation.isi??? 14
social impact