Issue 5, 2016

Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

Abstract

A 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.

Graphical abstract: Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

Supplementary files

Article information

Article type
Paper
Submitted
08 jul 2015
Accepted
22 okt 2015
First published
11 nov 2015

Dalton Trans., 2016,45, 2156-2171

Author version available

Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

I. Ara, J. Forniés, S. Ibáñez, P. Mastrorilli, S. Todisco and V. Gallo, Dalton Trans., 2016, 45, 2156 DOI: 10.1039/C5DT02593A

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