Synthesis and structural characterization of trimethylphosphine complexes of technetium(III)

Journal Article · Tue Nov 26 23:00:00 EST 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00024a035· OSTI ID:7017315

Watson, P L; Calabrese, J C; Ovenall, D W; Smith, R G ^[1]; Albanese, J A ^[2]

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1. E.I. du Pont de Nemours and Comp., Inc., Wilmington, DE (United States)
2. Univ. of Delaware, Newark (United States)

The first structurally characterized technetium(III) complexes containing trimethylphosphine as a ligand are reported. A novel cationic technetium(III) phosphine hydride complex was prepared by reaction of (Tc(S-tu){sub 6})(PF{sub 6}){sub 3} (tu = {eta}{sup 1}-S{double bond}C(NH{sub 2}){sub 2}) with excess trimethylphosphine in methanol. The complex, (TcH({eta}{sup 2}-N,S-NHC(NH{sub 2})S)(PMe{sub 3}){sub 4})(PF{sub 6}) (1) was characterized spectroscopically and crystallographically, and shown to contain the unusual bidentate ligand ({eta}{sup 2}-N,S-NHC(NH{sub 2})S){sup {minus}} and a hydride ligand. Stirring 1 in methanol-d{sub 4} led to formation of a spectroscopically identified technetium(III) deuteride. (TcD({eta}{sup 2}-N,S-NDC(ND{sub 2})S)(PMe{sub 3}){sub 4})(PF{sub 6}). Crystallographic data for 1 are as follows: monoclinic, Cc, a = 9.305 (2) {angstrom}, b = 16.726 (2) {angstrom}, c = 19.951 (3) {angstrom}, {beta} = 91.24{degree}, V = 3,104.4 {angstrom}{sup 3}, Z = 4, R = 0.062 (R{sub 2} = 0.060) for 2,043 observed reflections having F{sub o} > 3{sigma}(F{sub o}). Reaction of a Tc(V) substrate, (NBu{sub 4})(TcOCl{sub 4}), with excess trimethylphosphine yielded mer-TcCl{sub 3}(PMe{sub 3}){sub 3} (2). Crystals of 2 suitable for X-ray analysis were obtained by cocrystallizing 2 with triphenyl isocyanurate, ((phNCO){sub 3}). The resulting material, (mer-TcCl{sub 3}(PMe{sub 3}){sub 3})((PhNCO){sub 3}), crystallized in the orthorhombic space group Pnma in a unit cell of dimensions a = 18.461 (1) {angstrom}, b = 13.934 (2) {angstrom}, c = 14.035 (1) {angstrom}, V = 3,610.3 {angstrom}{sup 3}, and Z = 4, with R = 0.044 (R{sub w} = 0.039) for 3,699 observed reflections having F{sub o}> 3{sigma}(F{sub o}). The closest intermolecular distances revealed no bonding between the two components in the crystal, 2 and ((PhNCO){sub 3}).

• OSTI ID: 7017315
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:24; 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
550601 -- Medicine-- Unsealed Radionuclides in Diagnostics
62 RADIOLOGY AND NUCLEAR MEDICINE
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BOND ANGLE
BOND LENGTHS
CARBON 13
CARBON ISOTOPES
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
CHEMICAL SHIFT
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DEUTERIUM
DIFFRACTION
DIMENSIONS
ELECTROCHEMISTRY
EVEN-ODD NUCLEI
HOURS LIVING RADIOISOTOPES
HYDROGEN ISOTOPES
INFRARED SPECTRA
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LENGTH
LIGANDS
LIGHT NUCLEI
MASS SPECTRA
MONOCLINIC LATTICES
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORTHORHOMBIC LATTICES
OXYGEN COMPOUNDS
PERTECHNETATES
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
QUALITATIVE CHEMICAL ANALYSIS
RADIOISOTOPES
REFRACTORY METAL COMPOUNDS
SCATTERING
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TECHNETIUM 99
TECHNETIUM COMPLEXES
TECHNETIUM COMPOUNDS
TECHNETIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VOLTAMETRY
X-RAY DIFFRACTION
YEARS LIVING RADIOI