title: Cyclometallated Pt(II) and Pd(II) complexes with a trithiacrown ligand.
abstract: We report the synthesis and full characterization for a series of cyclometallated complexes of Pt(II) and Pd(II) incorporating the fluxional trithiacrown ligand 1,4,7-trithiacyclononane ([9]aneS3). Reaction of [M(C insertion mark N)(micro-Cl)]2 (M = Pt(II), Pd(II); C insertion mark N = 2-phenylpyridinate (ppy) or 7,8-benzoquinolinate (bzq)) with [9]aneS3 followed by metathesis with NH4PF6 yields [M(C insertion mark N)([9]aneS3)](PF6). The complexes [M(C insertion mark P)([9]aneS3)](PF6) (M = Pt(II), Pd(II); Cinsertion markP = [CH2C6H4P(o-tolyl)2-C,P]-) were synthesized from their respective [Pt(C insertion mark P)(micro-Cl)]2 or [Pd(C insertion mark P)(micro-O2CCH3)]2 (C insertion mark P) starting materials. All five new complexes have been fully characterized by multinuclear NMR, IR and UV-Vis spectroscopies in addition to elemental analysis, cyclic voltammetry, and single-crystal structural determinations. As expected, the coordinated [9]aneS3 ligand shows fluxional behavior in its NMR spectra, resulting in a single 13C NMR resonance despite the asymmetric coordination environment of the cyclometallating ligand. Electrochemical studies reveal irreversible one-electron metal-centered oxidations for all Pt(II) complexes, but unusual two-electron reversible oxidations for the Pd(II) complexes of ppy and bzq. The X-ray crystal structures of each complex indicate an axial M-S interaction formed by the endodentate conformation of the [9]aneS3 ligand. The structure of [Pd(bzq)([9]aneS3)](PF6) exhibits disorder in the [9]aneS3 conformation indicating a rare exodentate conformation as the major contributor in the solid-state structure. DFT calculations on [Pt([9]aneS3)(ppy)](PF6) and [Pd([9]aneS3)(ppy)](PF6) indicate the HOMO for both complexes is primarily dz2 in character with a significant contribution from the phenyl ring of the ppy ligand and p orbital of the axial sulfur donor. In contrast, the calculated LUMO is primarily ppy pi* in character for [Pt([9]aneS3)(ppy)](PF6), but dx2-y2 in character for [Pd([9]aneS3)(ppy)](PF6).
authors: Department of Chemistry, College of St. Catherine, St. Paul, MN 55105, USA. dejanzen@stkate.edu
authors: Daron E
authors: DE
authors: Janzen
authors: Donald G
authors: DG
authors: Vanderveer
authors: Larry F
authors: LF
authors: Mehne
authors: Demétrio A
authors: DA
authors: da Silva Filho
authors: Jean-Luc
authors: JL
authors: Brédas
authors: Gregory J
authors: GJ
authors: Grant
mesh_terms: D047248:Crown Compounds / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D047248:Crown Compounds; D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D010984:Platinum; D010165:Palladium