Structure of the tetra-n-butylammonium salt of the tetrachloro(methanol)nitrosyltechnetium(II) anion

Brown, D. S.; Newman, Josephine; Thornback, John R.; Davison, Alan

doi:10.1107/s0108270187090528

Cited by 16 publications

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“…The [TcCl 6 ] 2– counterion does not represent a decomposition product of the nitrosyl compound, but was contained in significant amounts in the starting material, which was prepared according to a not fully outlined literature procedure , . Such findings encouraged us to re‐investigate the synthesis of the common starting material (NBu 4 )[Tc II (NO)Cl 4 (MeOH)] with special attention to the complete removal of eventually formed hexachloridotechnetate(IV).…”

Section: Resultsmentioning

confidence: 99%

“…From such solutions, (NBu 4 )[Tc(NO)Cl 4 (MeOH)] can be obtained after slow evaporation of a CH 2 Cl 2 /MeOH mixture. The solid‐state structure of the methanol solvate of this complex has been published before by Thornback et al…”

Section: Resultsmentioning

confidence: 99%

“…Most of the compounds were prepared by ligand exchange reactions starting from (NBu 4 )[Tc(NO)Cl 4 (MeOH)]. Other approaches to technetium nitrosyls are reactions of common starting materials such as [TcO X 4 ] – , [Tc X 6 ] 2– ( X = Cl, Br), TcO 2 , or even TcO 4 – with NO gas or hydroxylamine hydrochloride . Other nitrosylation agents for technetium compounds are HNO 3 , NO 2 – , NO + salts or acetohydroxamic acid …”

Section: Introductionmentioning

confidence: 99%

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Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

Ackermann

Noufele

Hagenbach

et al. 2018

Zeitschrift anorg allge chemie

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

Ackermann

Noufele

Hagenbach

et al. 2018

Zeitschrift anorg allge chemie

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“…Subsequently, a convenient high-yield synthetic route to the versatile Tc(II)-containing material [n-Bu 4 N] [Tc(NO)Cl 4 ] was reported (Cheah et al 1987), prompting renewed interest in low-valent Tc-nitrosyl chemistry. Anionic Tc(II) species [Tc(NO)Cl 4 (MeOH)] - (Brown et al 1987) and [Tc(NO)Cl 4 (acac)] -(where acac is acetylacetone) (Brown et al 1988) as well as neutral [Tc(NO)Br 2 (CN t bu) 3 ] (where t bu is tert-butyl) (Linder et al 1986) complexes with distorted octahedral geometry were reported, suggesting the ability of the NO + ligand to stabilize the low-valent Tc(II) centers through π-back bonding leading to the delocalization of the Tc electron density. Similarly, stability of the Tc(III) complex [Tc(NO)(NH 3 )(phen) 2 ] 2+ (where phen is 1,10-phenanthroline) has also been attributed to the π-back-donation to the phenanthroline and NO + ligands (Lu and Clarke 1992).…”

Section: Technetium Nitrosyl Compoundsmentioning

confidence: 99%

Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report

Hall

Chatterjee

Levitskaia

et al. 2015

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Among long-lived radioactive constituents in the Hanford tank waste, Tc presents a unique challenge in that it exists predominantly in the liquid phase, generally in the anionic form of pertechnetate, TcO 4 -, which is highly volatile at low-activity waste (LAW) vitrification melter temperatures and mobile in the Hanford site's subsurface environment. The complex behavior of Tc under storage, treatment, and immobilization conditions significantly affects its management options, which to-date remain uncertain.In strongly alkaline environments, Tc exists as pertechnetate, TcO 4 -(oxidation state +7), and in the reduced forms (oxidation state < +7) collectively known as non-pertechnetate species. Pertechnetate is a well-characterized, anionic Tc species that can be removed from LAW by anion exchange or solvent extraction methods. There is no definitive information on the origin of the non-pertechnetate Tc species, nor is there a comprehensive description of their composition and behavior. It has been recently proposed that the non-pertechnetate species can comprise Tc(I) metal center and carbonyl or mixed carbonyl nitrosyl ligands stabilizing low-valent Tc. Recent work by our group has significantly expanded this previous work, generating a series of Tc(I) carbonyl compounds and demonstrating that they can be generated from reduction of TcO 4 in the simulated Hanford tank waste in presence of CO at elevated temperature (Levitskaia et al. 2014). These results are consistent with the previous proposal that [Tc(CO) 3 ] + species can be present in the Hanford tank waste and suggest that the low Tc(I) oxidation state is stabilized by the π-accepting ability of the CO ligands. The continuation work has been initiated to develop model Tc carbonyl nitrosyl compounds and investigate their potential presence in the Hanford tank wastes. This report summarizes our to-date results. Synthesis of the low-valent Tc carbonyl nitrosyl complexes was performed using two Tc(I) tricarbonyl precursors, namely monomeric [Tc(CO) 3 Cl 3 ] 2and tetrameric [Tc(CO) 3 (OH)] 4 species, in methylene chloride solvent using NOBF 4 as the nitrolysation reagent. Both pathways generated [Tc(CO) 2 (NO)] 2+ species as evident from the Tc-99 nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic characterization of the reaction products. The reaction yield using [Tc(CO) 3 Cl 3 ] 2starting material was about 70% with the Tc carbonyl nitrosyl species partitioned between the liquid and solid reaction fractions, and about 30% of starting Tc(I) oxidized to Tc(VII). The reaction yield using [Tc(CO) 3 (OH)] 4 starting material was nearly quantitative with Tc carbonyl nitrosyl product forming insoluble precipitate.The obtained results suggest that the Tc carbonyl nitrosyl product contained one monomeric [Tc(CO) 2 (NO)Cl 3 ]and two trans Cl-bridged dimeric [Tc(CO) 2 (NO)(μ-Cl)Cl] 2 species. However, this assignment should be validated by the future studies. Density functional theory (DFT) computational modeling supported the spectroscopic characterizatio...

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“…The reaction of the Tc(II) nitrosyl complex (Bu 4 N)[TcNOCl 4 ] [3] with stoichiometric amounts of 2-mercaptopyridine (HSpy) and a proton scavenger gives a mixture of products as determined by multiple absorptions in this region in the infrared spectroscopy of the crude product. However, the reaction of [TcCl 2 (NO)(HOMe)(PPh 3 ) 2 ] with a stoichiometric amounts of 2-mercaptopyridine and a proton scavenger gives a single product, [Tc(NO)CI(PPh 3 ) 2 (Spy)].…”

Section: Introductionmentioning

confidence: 99%

The synthesis and structural characterization of the technetium nitrosyl complexes [TcCl(NO)(SC5H4N)(PPh3)2] and [Tc(NO)(SC5H4N)2(PPh3)]

Nicholson

Mahmood

Müller

et al. 2011

Inorganica Chimica Acta

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The reaction of the Tc(I) complex [Tc(NO)Cl2(HOMe)(PPh3)2] with stoichiometric amounts of 2-mercatopyridine and a proton scavenger yields [Tc(NO)Cl(Spy)(PPh3)2] or [Tc(NO)(Spy)2(PPh3)], depending upon quantities of ligands employed. These two complexes have been structurally characterized. The small bite angles of the bidentate mercaptopyridine ligands cause significant deviation from octahedral coordination geometry.

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Structure of the tetra-n-butylammonium salt of the tetrachloro(methanol)nitrosyltechnetium(II) anion

Cited by 16 publications

References 1 publication

Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report

The synthesis and structural characterization of the technetium nitrosyl complexes [TcCl(NO)(SC5H4N)(PPh3)2] and [Tc(NO)(SC5H4N)2(PPh3)]

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