title: Synthesis of a Novel Class of Trigonal Bipyramidal Nitrido Tc(V) Complexes with Phosphino-Thiol Ligands. Crystal Structure of [(99g)Tc(N)(L(1))(2)] [L(1) = 2-(Diphenylphosphino)ethanethiolato] and [(99g)Tc(N)(L(5))(2)] [L(5) = 2-(Ditolylphosphino)propanethiolato].
abstract: Reactions of the precursor complexes [(99g)Tc(N)Cl(2)(PPh(3))(2)] and [(99g)Tc(N)Cl(4)](-) with phosphine-thiol ligands (HL(n)()) of the type R(2)PCH(2)CH(2)SH (R = phenyl, methoxypropyl), R(2)'PCH(2)CH(2)CH(2)SH (R' = phenyl, tolyl), and R(2)' 'P-o-C(6)H(4)SH (R' ' = phenyl) afforded the five-coordinated, disubstituted nitrido technetium(V) complexes [(99g)Tc(N)(L(n)())(2)]. The complexes were characterized by elemental analysis, (1)H and (31)P NMR spectroscopy, FT IR, and positive FAB MS spectra. Structural characterization of [(99g)Tc(N)(L(1))(2)] (1) [HL(1) = (C(6)H(5))(2)PCH(2)CH(2)SH] and [(99g)Tc(N)(L(5))(2)] (5) [HL(5) = (o-CH(3)C(6)H(4))(2)PCH(2)CH(2)CH(2)SH] showed that the bidentate phosphino-thiol ligands are coordinated to the technetium center through the neutral phosphorus atom and the deprotonated thiol sulfur atom. These complexes possess an uncommon trigonal bipyramidal geometry with the two phosphorus atoms occupying the two transaxial positions and the two sulfur atoms on the equatorial plane along with the nitrido nitrogen atom. Compound 1 crystallizes in the monoclinic space group C2/c, a = 24.84(2) Å, b = 7.327(6) Å, c = 31.52(2) Å, beta = 111.06(10) degrees, and Z = 8. Compound 5 crystallizes in the monoclinic space group P2(1)/n, a = 11.090(1) Å, b = 14.387(2) Å, c = 11.087(1) Å, beta = 113.62(1) degrees, and Z = 2.
authors.affiliation: Laboratorio di Medicina Nucleare, Dipartimento di Medicina Clinica e Sperimentale, Università di Ferrara, Via L. Borsari, 46, 44100 Ferrrara, Italy, ICTIMA CNR, Area della Ricerca, Corso Stati Uniti, 4, 35020 Padova, Italy, Dipartimento di Scienze Farmaceutiche, Università di Padova, Via Marzolo, 5, 35131 Padova, Italy, and CIS bio international, 91192 Gif-sur-Yvette, France.
authors.forename: Cristina
authors.initials: C
authors.lastname: Bolzati
authors.forename: Alessandra
authors.initials: A
authors.lastname: Boschi
authors.forename: Licia
authors.initials: L
authors.lastname: Uccelli
authors.forename: Erica
authors.initials: E
authors.lastname: Malagò
authors.forename: Giuliano
authors.initials: G
authors.lastname: Bandoli
authors.forename: Francesco
authors.initials: F
authors.lastname: Tisato
authors.forename: Fiorenzo
authors.initials: F
authors.lastname: Refosco
authors.forename: Roberto
authors.initials: R
authors.lastname: Pasqualini
authors.forename: Adriano
authors.initials: A
authors.lastname: Duatti