Synthesis of sulfido and oxo complexes of technetium(V) and rhenium(V) containing dithiolato and hydrotris(1-pyrazolyl)borato ligands. Crystal structures of dimeric bis([mu]-ethane-1,2-dithiolato)bis(ethene-1,2-dithiolato)technetium(IV) and [hydrotris(1-pyrazolyl)borato](ethane-1,2-dithiolato)oxorhenium(V)
- Istituto di Chimica e Tecnologia dei Radioelementi del CNR, Padova (Italy)
- Universita di Bologna (Italy)
- Universita di Padova (Italy)
The new technetium(V)sulfido complexes [TcS(edt)[sub 2]][sup [minus]] (1) and [TcSCl[sub 2](HB(pz)[sub 3])] (3) have been prepared and characterized. These species constitute the first examples of technetium complexes containing a terminal Tc[double bond]S bond. Complex 1 was obtained from [TcCl[sub 6]][sup 2[minus]] by reaction with ethane-1,2-dithiol (H[sub 2]edt), while 3 was formed from [TcOCl[sub 2](HB(pz)[sub 3])] by atom transfer from B[sub 2]S[sub 3]. The rhenium analog of complex 3, [ReSCl[sub 2](HB(pz)[sub 3])] (4), has been also prepared. In the synthesis of 1, the dimeric Tc(IV) complex [Tc[sub 2](edt)[sub 2](e[double bond]dt)[sub 2]] (2) (e[double bond]dt = ethene-1,2-dithiolato) was isolated by precipitation. 2 represents the first example of a technetium complex containing two terminal dithiolene and two bridged dithiolato ligands. The conversion of ethane-1,2-dithiolato to ethene-1,2-dithiolato in the reaction of preparation of 1 and 2 seems to play a key role in the formation of the [Tc[double bond]S][sup 3+] core. The X-ray crystal structure of complex 2 showed the Tc atom in a trigonal prismatic array. 2 crystallizes in the triclinic space group P[bar 1]. The reactions of various monothiols and dithiols with [MCl[sub 6]][sup 2[minus]] and [MOCl[sub 2](HB(pz)[sub 3])] (M = Tc, Re) are also discussed. The X-ray crystal structure of one product of these reactions, namely the complex [ReO(edt)(HB(pz)[sub 3])] (5), has been determined. 5 was monomeric with the Re atom in a distorted octahedral environment. It crystallizes in the monoclinic space group P2[sub 1]/c. 31 refs., 3 figs., 5 tabs.
- OSTI ID:
- 6236194
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:10; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHENIUM COMPLEXES
CRYSTAL STRUCTURE
RHENIUM OXIDES
TECHNETIUM COMPLEXES
CHEMICAL PREPARATION
LATTICE PARAMETERS
MONOCLINIC LATTICES
TRICLINIC LATTICES
X-RAY DIFFRACTION
CHALCOGENIDES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
RHENIUM COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties