The complex trans-[PtCl(PCy2)(PHCy2)(2)] (1) possesses a terminal phosphanido group (PCy2) and a chloride ligand, which render it a good candidate for the synthesis of phosphanido-bridged heterodimetallic species (PHCy2)(2)Pt(-PCy2)M-L by reaction either with carbonyl metalates, as metal-based nucleophiles, or with metal-based electrophiles. The heterodinuclear complexes [(PHCy2)(2)Pt(-PCy2)Co(CO)(3)](Pt-Co) (2), [(PHCy2)(2)Pt(-PCy2)Mo(CO)(2)Cp](Pt-Mo) (3), and [(PHCy2)(2)Pt(-PCy2)W(CO)(2)Cp](Pt-W) (4) are obtained by reaction of 1 with the carbonyl metalates Na[Co(CO)(4)], Na[Mo(CO)(3)Cp] and Na[W(CO)(3)Cp], respectively. Although 2 is reluctant to react with carbon monoxide, 3 and 4 are promptly carbonylated under ambient conditions to afford mixtures of the cis and trans isomers of [(PHCy2)(CO)Pt(-PCy2)M(CO)(2)Cp] (M = Mo or W), which interconvert through dissociation/reassociation of the CO ligand coordinated to the Pt centre. The reaction of 1 with AuCl(PPh3) leads to the formation of the trinuclear Pt2Au complexes cis- and trans-[{Cl(PHCy2)(2)Pt(-PCy2)}(2)Au]Cl (cis- and trans-[8]Cl), in which a Au atom bridges two molecules of 1 through the originally terminal phosphanide ligands.
Synthesis of Heterodimetallic Complexes by Reaction of a Terminal Phosphido Pt Complex with Metal-Based Nucleophiles and Electrophiles
2014
Abstract
The complex trans-[PtCl(PCy2)(PHCy2)(2)] (1) possesses a terminal phosphanido group (PCy2) and a chloride ligand, which render it a good candidate for the synthesis of phosphanido-bridged heterodimetallic species (PHCy2)(2)Pt(-PCy2)M-L by reaction either with carbonyl metalates, as metal-based nucleophiles, or with metal-based electrophiles. The heterodinuclear complexes [(PHCy2)(2)Pt(-PCy2)Co(CO)(3)](Pt-Co) (2), [(PHCy2)(2)Pt(-PCy2)Mo(CO)(2)Cp](Pt-Mo) (3), and [(PHCy2)(2)Pt(-PCy2)W(CO)(2)Cp](Pt-W) (4) are obtained by reaction of 1 with the carbonyl metalates Na[Co(CO)(4)], Na[Mo(CO)(3)Cp] and Na[W(CO)(3)Cp], respectively. Although 2 is reluctant to react with carbon monoxide, 3 and 4 are promptly carbonylated under ambient conditions to afford mixtures of the cis and trans isomers of [(PHCy2)(CO)Pt(-PCy2)M(CO)(2)Cp] (M = Mo or W), which interconvert through dissociation/reassociation of the CO ligand coordinated to the Pt centre. The reaction of 1 with AuCl(PPh3) leads to the formation of the trinuclear Pt2Au complexes cis- and trans-[{Cl(PHCy2)(2)Pt(-PCy2)}(2)Au]Cl (cis- and trans-[8]Cl), in which a Au atom bridges two molecules of 1 through the originally terminal phosphanide ligands.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
