Synthesis and characterization of technetium(V) complexes with amine, alcoholate, and chloride ligands

Journal Article · Wed Jul 13 04:00:00 EDT 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00287a010· OSTI ID:5729326

Pearlstein, R M; Lock, C J.L.; Faggiani, R; Costello, C E; Zeng, C H; Jones, A G; Davison, A ^[1]

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1. Massachusetts Institute of Technology, Cambridge (USA)

Two general routes for the preparation of technetium complexes with aromatic amine, chloride, and alkoxide ligands are presented. The reactions of the tetrachlorooxotechnetate(V) anion of (n-Bu{sub 4}N)(TcOCl{sub 4}) with pyridine in tetrahydrofuran/alcohol solvent or of the dioxotetrakis(pyridine)technetium(V) cation of (TcO{sub 2}(py){sub 4})Cl with LiCl in sulfuric acid/alcohol both yield a neutral alkoxydichlorooxobis(pyridine)technetium(V) complex. The same isomer appears to result from either route. The analogous thiazole derivatives may be prepared in a like manner. The complex chloro(1,2-ethanediolato)oxo(1,10-phenanthroline)technetium(V), TcOCl(C{sub 2}H{sub 4}O{sub 2})(C{sub 12}H{sub 8}N{sub 2}), is prepared from (n-Bu{sub 4}N)(TcOCl{sub 4}) with 1,2-ethanediol and 1,10-phenanthroline in methanol. This complex was characterized by ir, uv/vis, and {sup 1}H and {sup 99}Tc NMR spectroscopies and by fast atom bombardment mass spectrometry. Further insight into the bonding in this complex comes from the single-crystal x-ray structure determination. The space group is monoclinic, P2{sub 1}/c, with a = 7.440 (2) {angstrom}, b = 8.928 (3) {angstrom}, c = 21.355 (4) {angstrom}, {beta} = 92.48 (2){degree}, V = 1417.2 (7) {angstrom}{sup 3}, and Z = 4. The structure was solved by standard methods and refined to R = 0.051 and R{sub w} = 0.036 based on 1859 reflections. The oxo and chloride ligands are mutually cis in the highly distorted octahedral coordination sphere. The unusually long Tc-Cl bond length (2.418 (2) {angstrom}) is attributed to a trans influence exerted by the coordinated diolate. This effect combined with short lengths for the C-C bond (1.491 (1) {angstrom}) and for the O-Tc-O linkage (1.924 (4), 1.902 (3) {angstrom}) suggests partial multiple bonding between the technetium and the diolate. 38 references, 2 figures, 3 tables.

• OSTI ID: 5729326
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 27:14; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALCOHOLS
AMINES
BARYONS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HADRONS
HALIDES
HALOGEN COMPOUNDS
HOURS LIVING RADIOISOTOPES
HYDROXY COMPOUNDS
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
MASS SPECTROSCOPY
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PROTONS
RADIOISOTOPES
SPECTRA
SPECTROSCOPY
SYNTHESIS
TECHNETIUM 99
TECHNETIUM COMPLEXES
TECHNETIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
YEARS LIVING RADIOISOTOPES