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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Selective Functionalization with Organophosphite Ligands of Atomically Precise Platinum Chini Clusters
Francesca Forti1, Cristiana Cesari1, Marco Bortoluzzi2
1Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Via P. Gobetti 85, Bologna 40129 Italy.
Abstract:
Heteroleptic [Pt3n(CO)6n-x{P(OR)3}x]2- (n = 3-5; x = 1, 2; R = Me, Et, Ph) Chini clusters have been obtained upon reaction of homoleptic [Pt3n(CO)6n]2- (n = 3-5) species with increasing amounts of P(OR)3. In the case of P(OPh)3, the whole series of clusters [Pt3n(CO)6n-x{P(OPh)3}x]2- (n = 3-5; x = 1, 2) has been spectroscopically characterized. In contrast, by using the stronger σ-bases P(OMe)3 and P(OEt)3, it has been possible to identify only the species [Pt12(CO)22{P(OR)3}2]2-, [Pt9(CO)17{P(OR)3}]2- and [Pt9(CO)16{P(OR)3}2]2- (R = Me, Et). Generally speaking, 1-2 CO ligands may be selectively replaced by P(OR)3 ligands in homoleptic [Pt3n(CO)6n]2- (n = 3-5) clusters, whereas the addition of a third P(OR)3 ligand results in the elimination of a Pt3-triangle and the concomitant formation of a smaller [Pt3(n-1)(CO)6(n-1)]2- cluster that may be further substituted. The nature in solution of all the species has been elucidated by means of FT-IR, ESI-MS, 1H and 31P{1H} NMR spectroscopy. The molecular structures of [PMePh3]2[Pt9(CO)17{P(OPh)3}]·CH3COCH3, [PMePh3]2[Pt12(CO)22{P(OPh)3}2]·solv, [PMePh3]2[Pt12(CO)22{P(OMe)3}2], [PMePh3]2[Pt15(CO)28{P(OPh)3}2]·2CH3COCH3·C6H14 have been determined by single-crystal X-ray diffraction (SC-XRD). Computational studies have been carried out to get insights into the torsional isomers of [Pt12(CO)22{P(OR)3}2]2- (R = Me, Ph) and the positional isomers of [Pt9(CO)18-x{P(OMe)3}x]2- (x = 1-3) and related species.
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