From a di- and trinuclear phosphanido fragment to tetra- and hexanuclear platinum(II) complexes

The di- and trinuclear derivatives [(RF)2Pt(μ- PPh2)2Pt(CH3CN)2], 1, [(R F)2Pt(μ-PPh2)2Pt(μ-PPh 2)2Pt(CH3CN)2], 2, (RF = C6F5) behave as synthons of di- and trinuclear fragments. Addition of azide and oxalate ions to 1 and 2, even in an excess, provides a way to isolate the tetranuclear and hexanuclear platinum complexes [NBu 4]2[{(RF)2Pt{(μ-PPh 2)2Pt}n(μ-1,1-N3)}2] (n = 1, 3; 2, 5), [NBu4]2[{(RF) 2Pt(μ-PPh2)2Pt}2(μ-C 2O4-κ2O,O′: κ 2O″,Oâ€́)}], 4, and [NBu4] 2[{(RF)2Pt(μ-PPh2) 2Pt(μ-PPh2)2Pt}2(μ-C 2O4-κ2O,O′: κ 2O″,Oâ€́)}], 6. The structures of 3-6, determined by single crystal X-ray diffraction, show a linear arrangement of the platinum centres maintained through >Pt(μ-PPh2) 2Pt> and >Pt(μ-1,1-N3)2Pt> or >Pt(μ-C2O4-κ2O,O′: κ2O″,Oâ€́)Pt> bridging fragments. Finally, addition of KCN to 2 affords the trinuclear [NBu4] 2[(RF)2Pt(μ-PPh2) 2Pt(μ-PPh2)2Pt(CN)2], 7, in which two cyanido groups are bonded to the platinum centre in a terminal way. © 2013 Elsevier B.V. All rights reserved.This work was supported by the Spanish MICINN (DGPTC)/FEDER (Project CTQ2008-06669-C02-01/BQU), MINECO/FEDER (Project CTQ2012-35251) and the Gobierno de Aragón (Grupo Consolidado E21: Química Inorgánica y de los Compuestos Organometálicos). A. A. gratefully acknowledges MICINN for a FPU grant.Peer Reviewe