New pentafluorophenyl complexes with phosphine-amide ligands |
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| Institution: | 1. Departamento de Química Inorgánica, Universidad de Murcia, 30071 Murcia, Spain;2. Departamento de Ingeniería Minera, Geológica y Cartográfica, Area de Química Inorgánica, 30203 Cartagena, Spain;1. School of Chemical Engineering, University of Science and Technology Liaoning (USTL), Anshan 114051, People’s Republic of China;2. State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics, Fine Mechanics and Physics (CIOMP), Chinese Academy of Sciences, Changchun 130033, People’s Republic of China;1. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India;2. Department of Chemistry, Howard University, Washington DC, 20059, USA;1. Universität zu Köln, Department für Chemie, Institut für Anorganische Chemie, Greinstrasse 6, D-50939 Köln, Germany;2. School of Chemistry, Monash University, PO Box 23, VIC 3800, Australia;1. Alma College, Department of Chemistry, Alma, MI 48801, USA;2. Michigan State University, Department of Chemistry and Biochemistry, East Lansing, MI 48824, USA;3. University of Missouri-Columbia, Department of Chemistry, Columbia, MO 65211, USA;1. Department of Chemistry, Texas A&M University, PO Box 30012, College Station, TX 77842-3012, USA;2. Institut für Organische Chemie and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054 Erlangen, Germany |
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| Abstract: | A series of nickel(II) and palladium(II) complexes containing one or two pentafluorophenyl ligands and the phosphino-amides o-Ph2PC6H4CONHR R = iPr (a), Ph (b)] displaying different coordination modes have been synthesised. The chelating ability of these ligands and the influence of both coligands and the metal centre in their potential hemilabile behaviour have been explored. The crystal structure of (b) has been determined and reveals N–H?O intermolecular hydrogen bonding. Bis-pentafluorophenyl derivatives M(C6F5)2(o-Ph2PC6H4CO-NHR)] M = Ni; R = iPr (1a); R = Ph (1b); M = Pd; R = iPr (2a); R = Ph (2b)] in which (a) and (b) act as rigid P, O-chelating ligands were readily prepared from the labile precursors cis-M(C6F5)2(PhCN)2]. X-ray structures of (1a), (1b) and (2a) have been established, allowing an interesting comparative structural discussion. Dinuclear {Pd(C6F5)(tht)(μ-Cl)}2] reacted with (a) and (b) yielding the monopentafluorophenyl complexes Pd(C6F5)Cl{PPh2(C6H4–CONH–R)}] (R = iPr (3a), Ph (3b)) that showed a P, O-chelating behaviour of the ligands, confirmed by the crystal structure determination of (3a). New cationic palladium(II) complexes in which (a) and (b) behave as P-monodentate ligands have been synthesised by reacting them with {Pd(C6F5)(tht)(μ-Cl)}2], stoichiometric Ag(O3SCF3) and external chelating reagents such as cod Pd(C6F5)(cod){PPh2(C6H4-CONH-R)}](O3SCF3)(R = iPr (4a), Ph (4b)) and 2,2′-bipy Pd(C6F5)(bipy){PPh2(C6H4-CONH-R)}](O3SCF3) (R = iPr (5a), Ph (5b)). When chloride abstraction in {Pd(C6F5)(tht)(μ-Cl)}2] is promoted by means of a dithioanionic salt as dimethyl dithiophospate in the presence of (a) or (b), the corresponding neutral complexes Pd(C6F5){S(S)P(OMe)2}{PPh2(C6H4-CONH-R)}] (R = iPr (6a), Ph (6b)) were obtained. |
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