doi:10.1039/c5dt02593aengAra, I.Forniés, J.Ibáñez, S.Mastrorilli, P.Todisco, S.Gallo, V.Polynuclear platinum phosphanido/phosphinito complexes: Formation of P-O and P-O-P bonds through reductive coupling processesART-2016-93621A mixture of the asymmetric complexes of formula (RF)2Pt(µ-Ph2PO)(µ-PPh2)Pt(µ-PPh2)2Pt(solv)(solv')] (1-(solv)(solv')] (solv, solv' = acetone, H2O, CH3CN) has been prepared by reaction of (RF)2PtII(µ-PPh2)2PtII(µ-PPh2)2PtII(NCCH3)2] with AgClO4 in CH3CN/acetone. The lability of the Pt-solvent bonds allows the displacement of the coordinated solvent molecules by dppm or Cl- and the isolation of the tri- or hexanuclear phosphanido/phosphinito Pt(ii) complexes (C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(dppm)] (2) or NBu4]2(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(µ-Cl)2Pt(µ-PPh2)2Pt(µ-PPh2)(µ-PPh2O)Pt(C6F5)2] (as a mixture of the two possible isomers 4a and 4b). Complex 2 reacts with AgClO4 to form the tetranuclear derivative (C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(dppm)Ag(OClO3)] (3), which displays two Pt-Ag donor-acceptor bonds. The mixture of the hexanuclear isomers 4a-4b reacts with Tl(acac) producing the acetylacetonato complex NBu4](C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(acac)] (5) which, upon reaction with HCl, yields back the mixture of 4a-4b. The reaction of 4a-4b with PPh3 produces NBu4](C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(Cl)(PPh3)] (6) as a mixture of isomers with the chloro ligand located syn (6a) or anti (6b) to the PPh2O- group. Either the reaction of 6 with AgClO4 or the treatment of 5 with HPPh3ClO4 results in the formation of the species (C6F5)2PtII(µ-PPh2)2PtI(µ-PPh2OPPh2)PtI(PPh3)] (7) (44 VEC), which can be explained as the consequence of a PPh2O/PPh2 reductive coupling and a rearrangement of ligands in the molecule generating a Pt(ii), Pt(i), Pt(i) compound. All complexes were characterised in the solid state by XRD (only one of the isomers, in the cases of 4 and 6) and in solution by NMR spectroscopy.2016http://zaguan.unizar.es/record/16823910.1039/c5dt02593ahttp://zaguan.unizar.es/record/168239oai:zaguan.unizar.es:168239Dalton Transactions 45, 5 (2016), 2156-2171All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/closedAccess