title: Coordination chemistry of dinucleating P2N2S ligands: preparation and characterization of cationic palladium complexes.
abstract: The thioethers (4-tert-butyl-2,6-bis((2-(diphenylphosphino)ethylimino)methyl)phenyl)(tert-butyl)sulfane (tBuL3) and (4-tert-butyl-2,6-bis((2-(diphenylphosphino)ethylamino)methyl)phenyl)(tert-butyl)sulfane (tBuL4) react readily with [Pd(NCMe)2Cl2] to give the dinuclear palladium thiophenolate complexes [(L3)Pd2(Cl)2]+ and [(L4)Pd2(micro-Cl)]2+ (HL3=2,6-bis((2-(diphenylphosphino)ethylimino)methyl)-4-tert-butylbenzenethiol, HL4=2,6-bis((2-(diphenylphosphino)ethylamino)methyl)-4-tert-butylbenzenethiol). The chlorides in could be replaced by neutral (MeCN) and anionic ligands (NCS-, N3-, I-, CN-) to give the dinuclear PdII complexes [(L3)Pd2(NCMe)2]3+, [(L3)Pd2(SCN)2]+, [(L3)Pd2(N3)2]+, [(L3)Pd2(I)2]+, and [(L3)Pd2(CN)2]+. The acetonitrile ligands in are readily hydrated to give the corresponding amidato complex [(L3)Pd2(NHCOMe)]2+. All complexes were isolated as perchlorate salts and studied by infrared, 1H, and 31P NMR spectroscopy. In addition, complexes [ClO4].EtOH, [ClO4]2, [ClO4], [ClO4].EtOH, and [ClO4]2.MeCN.MeOH have been characterized by X-ray crystallography. The dipalladium complex was found to catalyse the vinyl-addition polymerization of norbornene in the presence of MAO (methylalumoxane) and B(C6F5)3/AlEt3.
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, D-04103, Leipzig, Germany.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Siedle
authors.forename: Paul-Gerhard
authors.initials: PG
authors.lastname: Lassahn
authors.forename: Vasile
authors.initials: V
authors.lastname: Lozan
authors.forename: Christoph
authors.initials: C
authors.lastname: Janiak
authors.forename: Berthold
authors.initials: B
authors.lastname: Kersting
mesh_terms: D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D002412:Cations; D008024:Ligands; D009942:Organometallic Compounds; D010165:Palladium