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Issue 6, 2017
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Cyclometalated platinum(ii) complexes of 2,2′-bipyridine N-oxide containing a 1,1′-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies

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Abstract

The preparation and characterization of new heteronuclear-platinum(II) complexes containing a 1,1′-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ2N,C-bipyO-H)(SMe2)], A, in which bipyO-H is a cyclometalated rollover 2,2′-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of the corresponding binuclear complex [Pt2Me22N,C-bipyO-H)2(μ-dppf)], 1, or the mononuclear complex [PtMe(κ1C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelating ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by the single-crystal X-ray diffraction method and it was shown that the chelating dppf ligand in this complex was arranged in a “synclinal–staggered” conformation. Also, the occurrence of intermolecular C–HCp⋯ObipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.

Graphical abstract: Cyclometalated platinum(ii) complexes of 2,2′-bipyridine N-oxide containing a 1,1′-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies

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Supplementary files

Article information


Submitted
24 Oct 2016
Accepted
12 Jan 2017
First published
13 Jan 2017

Dalton Trans., 2017,46, 2013-2022
Article type
Paper

Cyclometalated platinum(II) complexes of 2,2′-bipyridine N-oxide containing a 1,1′-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies

H. R. Shahsavari, M. Fereidoonnezhad, M. Niazi, S. T. Mosavi, S. Habib Kazemi, R. Kia, S. Shirkhan, S. Abdollahi Aghdam and P. R. Raithby, Dalton Trans., 2017, 46, 2013
DOI: 10.1039/C6DT04085C

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