Dalton Transactions (RSC Publishing)

Synthesis and characterisation of new binuclear complexes containing a relatively strong Pt to Hg donor bond. Molecular structure of complex [Pt(C^P)(μ-O2CCH3)2Hg(O2CCH3)]

Irene Ara,a Juan Forniés,*a Violeta Siciliab and Pablo Villarroyaa Author affiliations

* Corresponding authors

a Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C., Pedro Cerbuna 12, 50009 Zaragoza, Spain

b Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Escuela Universitaria de Ingeniería Técnica Industrial, Universidad de Zaragoza-C.S.I.C., Campus Universitario del Actur, Edificio Torres Quevedo, 50018 Zaragoza, Spain

Abstract

[{Pt(C^P)(μ-O2CCH3)}2] (1A) (C^P = CH2-C6H4-P(o-tolyl)2-κC,P) reacts with Hg(O2CCH3)2 and [{Pt(C^P)(μ-O2CCF3)}2] (1B) reacts with Hg(O2CCF3)2 in a 1 ∶ 2 molar ratio to afford the neutral complexes [Pt(C^P)(μ-O2CCH3)2Hg(O2CCH3)] (2) and [Pt(C^P)(μ-O2CCF3)2Hg(O2CCF3)] (3) respectively. They also react with equimolar amounts of HgX2 (X = Cl, Br, I) to give mixtures of the corresponding neutral complexes [Pt(C^P)(μ-O2CR)2HgX] (R = CH3, X = Cl 4, Br 5, I 6; R = CF3, X = Cl 7, Br 8, I 9) and [{Pt(C^P)(μ-X)}2] (X = Cl, Br, I). Complexes 4–6 could be isolated from the mixtures as pure samples but complexes 7–9 could not. Complexes [Pt(C^P)(μ-O2CR)2HgX] (R = CH3, X = Cl 4, Br 5, I 6; R = CF3, X = Cl 7, Br 8, I 9) can also be prepared by treatment of the carboxylate derivatives [Pt(C^P)(μ-O2CR)2Hg(O2CR)] (R = CH32, CF33) with methanol solutions of HX (X = Cl, Br, I) in 1 ∶ 1 molar ratio, this being the only way to obtain pure samples of complexes 7–9. The study of the molecular structure of 2 by X-ray diffraction reveals the existence of a very strong Pt to Hg donor bond (Pt–Hg = 2.6131(6) Å ). The NMR data of 2 are in agreement with its observed structure in the solid state. The similarity of the NMR data of all complexes leads us to propose the same structure for all of them, which seems to be retained in solution at room temperature.

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