title: Synthesis, catalytic activity, and photophysical properties of 5,6-membered Pd and Pt SCS'-pincer complexes based on thiophosphorylated 3-amino(hydroxy)benzoic acid thioanilides.
abstract: Novel unsymmetrical SCS'-pincer ligands, 1-[PhNHC(S)]-3-[Ph(2)P(S)NH]-C(6)H(4) (3) and 1-[PhNHC(S)]-3-[Ph(2)P(S)O]C(6)H(4) (7), bearing a thiocarbamoyl moiety in combination with thiophosphorylamino- and thiophosphoryloxy-donating groups, respectively, were obtained via thiophosphorylation of 3-amino- and 3-hydroxy-benzoic acid (thio)anilides 1 and 6. Direct cyclometallation of the central benzene ring in the ligands 3 and 7 in reaction with (PhCN)(2)MCl(2) (M = Pd, Pt) as a metal precursor afforded κ(3)-SCS'-hybrid pincer complexes 8, 9 with 5- and 6-membered fused metallacycles in good to high yields (67-95%). The complexes 8 and 9 were characterized by multinuclear NMR ((31)P, (1)H, (13)C) and IR spectroscopy as well as single-crystal X-ray crystallography. Palladium complexes 8a and 9a were shown to be active catalysts for the Suzuki-Miyaura cross-coupling reaction. In the solid state the ligands 3 and 7 as well as their Pt(II) and Pd(II) complexes 8 and 9 are luminescent at 300 K. The emission of the complexes has the different origin depending on the metal nature.
authors.affiliation: A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia.
authors.forename: D V
authors.initials: DV
authors.lastname: Aleksanyan
authors.forename: V A
authors.initials: VA
authors.lastname: Kozlov
authors.forename: Y V
authors.initials: YV
authors.lastname: Nelyubina
authors.forename: K A
authors.initials: KA
authors.lastname: Lyssenko
authors.forename: L N
authors.initials: LN
authors.lastname: Puntus
authors.forename: E I
authors.initials: EI
authors.lastname: Gutsul
authors.forename: N E
authors.initials: NE
authors.lastname: Shepel
authors.forename: A A
authors.initials: AA
authors.lastname: Vasil'ev
authors.forename: P V
authors.initials: PV
authors.lastname: Petrovskii
authors.forename: I L
authors.initials: IL
authors.lastname: Odinets
mesh_terms: D000813:Anilides / Q000737:chemistry*; D001565:Benzoates / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010777:Photochemistry; D013237:Stereoisomerism
chemical_list: D000813:Anilides; D001565:Benzoates; D009942:Organometallic Compounds; D010165:Palladium