Unusual Metal-Metal Bonding in a Dinuclear Pt-Au Complex: Snapshot of a Transmetalation Process

Miguel Baya; Úrsula Belío; Israel Fernández; Sara Fuertes; Antonio Martín

doi:10.1002/anie.201602081

Unusual Metal-Metal Bonding in a Dinuclear Pt-Au Complex: Snapshot of a Transmetalation Process

Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6978-82. doi: 10.1002/anie.201602081. Epub 2016 Apr 25.

Authors

Miguel Baya¹, Úrsula Belío¹, Israel Fernández², Sara Fuertes¹, Antonio Martín³

Affiliations

¹ Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, C/ Pedro Cerbuna 12, 50009, Zaragoza, Spain.
² Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain.
³ Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, C/ Pedro Cerbuna 12, 50009, Zaragoza, Spain. tello@unizar.es.

PMID: 27111913
DOI: 10.1002/anie.201602081

Abstract

The dinuclear Pt-Au complex [(CNC)(PPh3 )Pt Au(PPh3 )](ClO4 ) (2) (CNC=2,6-diphenylpyridinate) was prepared. Its crystal structure shows a rare metal-metal bonding situation, with very short Pt-Au and Au-Cipso (CNC) distances and dissimilar Pt-Cipso (CNC) bonds. Multinuclear NMR spectra of 2 show the persistence of the Pt-Au bond in solution and the occurrence of unusual fluxional behavior involving the [Pt(II) ] and [Au(I) ] metal fragments. The [Pt(II) ]⋅⋅⋅ [Au(I) ] interaction has been thoroughly studied by means of DFT calculations. The observed bonding situation in 2 can be regarded as a model for an intermediate in a transmetalation process.

Keywords: DFT calculations; donor-acceptor systems; fluxionality; heterobimetallic complexes; metal-metal bonds.

Publication types

Research Support, Non-U.S. Gov't