Rhenium(V) and technetium(V) complexes of bidentate (O, O) monobasic 3-oxy-4-pyronato and -4-pyridinonato ligands. X-ray structures of cis-bromobis(3-methyl-2-oxy-4-pyronato)oxorhenium(V), tetra-n-butylammonium tribromo(3-methyl-2-oxy-4-pyronato)oxorhenate(V), and tetra-n-butylammonium trichloro(3-methyl-2-oxy-4-pyronato)oxotechnetate(V)

Journal Article · Wed Oct 13 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00073a005· OSTI ID:7072267

Luo, H; Rettig, S J; Orvig, C ^[1]

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1. Univ. of British Columbia, Vancouver (Canada)

A series of technetium(V) and rhenium(V) complexes of the form [MOXL[sub 2]], where L is a bidentate (O, O) monobasic ligand, 2-methyl-3-oxy-4-pyronate (maltolate, ma[sup [minus]]) or 1,2-dimethyl-3-oxy-4-pyridinonate (dpp[sup [minus]]), and X is a halo ligand, X = Cl (M = Tc) or Br (M = Re), have been synthesized by ligand substitution on [TcOCl[sub 4]][sup [minus]] or [ReOBr[sub 4]][sup [minus]] anions in nonaqueous solutions. Trihalo(maltolato)oxometalate complexes of technetium(V) and rhenium(V), [MOX[sub 3](ma)][sup [minus]] (M = Tc, X = Cl; M = Re, X = Br), were also prepared as tetra-n-butylammonium (M = Tc, Re) or tetraphenylarsonium (M = Re) salts. The complexes have been studied by IR, [sup 1]H NMR, and mass spectra. The X-ray structures of [ReOBr(ma)[sub 2]], [(n-Bu)[sub 4]N][ReOBr[sub 3](ma)] and [(n-Bu)[sub 4]N][TcOCl[sub 3](ma)] were determined. Crystals of [ReOBr(ma)[sub 2]] (C[sub 12]H[sub 10]BrO[sub 7]Re) are triclinic, and Z = 4. For [ReOBr-(ma)[sub 2]], the solution of [sup 1]H NMR spectrum and the crystal structure both demonstrate cis-geometry, with the Re atom being in the center of a highly distorted octahedron of cis-(bromo, oxo) donors and ketonic oxygen and hydroxy oxygen donors of the two mutually orthogonal maltolato ligands. In [(n-Bu)[sub 4]N][ReOBr[sub 3](ma)] and [(n-Bu)[sub 4]N][TcOCl[sub 3](ma)], the [MOX[sub 3](ma)][sup [minus]] anions are isostructural; the metal atom is also in a highly distorted octahedral environment in each case, with the maltol hydroxy oxygen trans to the oxo group.

• OSTI ID: 7072267
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:21; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
MAGNETIC RESONANCE
MASS SPECTROSCOPY
NUCLEAR MAGNETIC RESONANCE
RESONANCE
RHENIUM COMPLEXES
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TECHNETIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TRICLINIC LATTICES