title: Cyclometalated platinum(ii) complexes of 2,2'-bipyridine N-oxide containing a 1,1'-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies.
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 [Pt2Me2(κ2N,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-HCpObipyO-Hinteractions 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.
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Yousef Sobouti Blvd., Zanjan 45137-6731, Iran. shahsavari@iasbs.ac.ir.
authors.forename: Hamid R
authors.identifier: http://orcid.org/0000-0002-2579-2185
authors.initials: HR
authors.lastname: Shahsavari
authors.affiliation: Department of Medicinal Chemistry, School of Pharmacy, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran. fereidoonnezhad-m@ajums.ac.ir and Cancer, Environmental and Petroleum Pollutants Research Center, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran.
authors.forename: Masood
authors.initials: M
authors.lastname: Fereidoonnezhad
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Yousef Sobouti Blvd., Zanjan 45137-6731, Iran. shahsavari@iasbs.ac.ir.
authors.forename: Maryam
authors.initials: M
authors.lastname: Niazi
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Yousef Sobouti Blvd., Zanjan 45137-6731, Iran. shahsavari@iasbs.ac.ir.
authors.forename: S Talaat
authors.initials: ST
authors.lastname: Mosavi
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Yousef Sobouti Blvd., Zanjan 45137-6731, Iran. shahsavari@iasbs.ac.ir.
authors.forename: Sayed
authors.initials: S
authors.lastname: Habib Kazemi
authors.affiliation: Chemistry Department, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran. rkia@sharif.edu.
authors.forename: Reza
authors.initials: R
authors.lastname: Kia
authors.affiliation: Department of Medicinal Chemistry, School of Pharmacy, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran. fereidoonnezhad-m@ajums.ac.ir.
authors.forename: Shima
authors.initials: S
authors.lastname: Shirkhan
authors.affiliation: Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Yousef Sobouti Blvd., Zanjan 45137-6731, Iran. shahsavari@iasbs.ac.ir.
authors.forename: Siamak
authors.initials: S
authors.lastname: Abdollahi Aghdam
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, Avon BA2 7AY, UK.
authors.forename: Paul R
authors.identifier: http://orcid.org/0000-0002-2944-0662
authors.initials: PR
authors.lastname: Raithby