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Title: 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)

Abstract

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 onemore » 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.« less

Authors:
; ;  [1];  [2];  [3]
  1. (Istituto di Chimica e Tecnologia dei Radioelementi del CNR, Padova (Italy))
  2. (Universita di Bologna (Italy))
  3. (Universita di Padova (Italy))
Publication Date:
OSTI Identifier:
6236194
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; (United States); Journal Volume: 32:10
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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

Citation Formats

Tisato, F., Bolzati, C., Refosco, F., Duatti, A., and Bandoli, G. 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). United States: N. p., 1993. Web. doi:10.1021/ic00062a028.
Tisato, F., Bolzati, C., Refosco, F., Duatti, A., & Bandoli, G. 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). United States. doi:10.1021/ic00062a028.
Tisato, F., Bolzati, C., Refosco, F., Duatti, A., and Bandoli, G. Wed . "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)". United States. doi:10.1021/ic00062a028.
@article{osti_6236194,
title = {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)},
author = {Tisato, F. and Bolzati, C. and Refosco, F. and Duatti, A. and Bandoli, G.},
abstractNote = {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.},
doi = {10.1021/ic00062a028},
journal = {Inorganic Chemistry; (United States)},
number = ,
volume = 32:10,
place = {United States},
year = {Wed May 12 00:00:00 EDT 1993},
month = {Wed May 12 00:00:00 EDT 1993}
}