Cyclometalated platinum(ii) complexes of 2, 2′-bipyridine N-oxide containing a 1, 1′-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies12. Issue 6 (24th January 2017)

• Record Type: Journal Article
• Authors: Shahsavari, Hamid R.; Fereidoonnezhad, Masood; Niazi, Maryam; Mosavi, S. Talaat; Habib Kazemi, Sayed; Kia, Reza; Shirkhan, Shima; Abdollahi Aghdam, Siamak; Raithby, Paul R.
• Is Part Of: Dalton transactions. Volume 46:Issue 6(2017)
• Page Start: 2013
• Page End: 2022
• Publication Date: 2017-01-24
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt04085c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Two cycloplatinated rollover complexes containing dppf ligand were synthesized and characterized. 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(κ 2 N, 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 [Pt2 Me2 (κ 2 N, C -bipyO-H)2 (μ-dppf)], 1, or the mononuclear complex [PtMe(κ 1 C -bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in1 and2 behaves as either a bridging or chelating ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of2 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 in2 was performed.