[TcII(NO)(trifluoroacetate)4F]2−– synthesis and reactions

Balasekaran, Samundeeswari Mariappan; Hagenbach, Adelheid; Drees, Markus; Abram, Ulrich

doi:10.1039/c7dt03084c

Cited by 23 publications

(30 citation statements)

References 47 publications

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“…All attempts to obtain a 99 Tc NMR signal failed. This is unusual for technetium(I) complexes, but in a line with the related compound [Tc(NO)Cl 2 (H 2 L2) 2 ] . The same holds true for the 31 P NMR spectra of 1 and [Tc(NO)Cl 2 (H 2 L2) 2 ].…”

Section: Resultssupporting

confidence: 57%

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

Ackermann

Noufele

Hagenbach

et al. 2018

Zeitschrift anorg allge chemie

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Section: Resultssupporting

confidence: 57%

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

Ackermann

Noufele

Hagenbach

et al. 2018

Zeitschrift anorg allge chemie

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“…1.23 Å) bond lengths indicate delocalization of the electron density in the pseudoallyl system. The Tc–O4 bond lengths of 2.184(4) Å in the η 1 -formato and 2.162(3) Å in the η 1 -trifluoroacetato complex are in the range of the technetium–oxygen single bond in the previously studied trifluoroacetato complexes. ,, …”

Section: Resultsmentioning

confidence: 99%

Technetium Hydrides Revisited: Syntheses, Structures, and Reactions of [TcH₃(PPh₃)₄] and [TcH(CO)₃(PPh₃)₂]

2021

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Optimized synthetic approaches to [TcH 3 (PPh 3 ) 4 ] (1) and mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) as key compounds of the technetium hydrido chemistry are reported. They give access to pure and stable samples of the complexes. The solid-state structures of the two title compounds have been determined. Reactions of [TcH 3 (PPh 3 ) 4 ] with monodentate basic phosphines such as PMe 2 Ph or PMe 3 lead to mixtures o f m i x e d -p h o s p h i n e c o m p l e x e s o f t h e c o m p o s i t i o n s [TcH 3 (PR 3 ) n (PPh 3 ) 4−n ] (n = 1−3), from which the mixed-phosphine trihydride complex [TcH 3 (PPh 3 ) 2 (PMe 3 ) 2 ] (2) could be isolated. Spectroscopic data and DFT calculations suggest a fluxional structure between a capped trigonal prism and a pentagonal bipyramid. Reactions of the monohydride mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) with HX (X = Cl, Br, I) give [TcX(CO) 3 (PPh 3 ) 2 ] (6) complexes in good yields, while mer-trans-[Tc{η 1 -O(CR)O}(CO) 3 (PPh 3 ) 2 ] (7) or cis−trans-[Tc{η 2 -OO(CR)}(CO) 2 (PPh 3 ) 2 ] (8) complexes are formed with carboxylic acids depending on the substituent R and the conditions applied. Chelate formation of the formato ligand can also be obtained by thermal decarbonylation of the isolated mertrans-[Tc(η 1 -O(CH)O)(CO) 3 (PPh 3 ) 2 ] (7a) complex. The latter reaction is reversible, and the tricarbonyl compound is reformed when [Tc{η 2 -OO(CH)}(CO) 2 (PPh 3 ) 2 ] (8a) is exposed to CO gas. Reactions of [TcH(CO) 3 (PPh 3 ) 2 ] (5) with phenyl seleninic acid (PhSeOOH) in methanol give the tetranuclear cluster [{Tc(CO) 3 } 3 (μ 3 -OH)(μ 2 -O(SePh)O) 3 {Tc(CO) 3 }] (10) and a small amount of the bridged dinuclear oxalato complex [Tc 2 (CO) 6 (ox)(OPPh 3 ) 2 ] (11). The latter compound is the result of a complex reaction, which involves a metal-induced oxidation of methanol to formate and a subsequent C−C coupling of two formato ligands. The plausibility of the proposed mechanism is supported by the fact that the dimeric oxalato complex is much more efficiently formed when the formato complex [Tc{η 1 -O(CH)O}(CO) 3 (PPh 3 ) 2 ] (7a) is directly reacted with PhSeOOH. Exclusively the monomeric oxalato complex [Tc(η 2 -oxH)(CO) 2 (PPh 3 ) 2 ] ( 12) is formed during a reaction of mer-trans-[TcH(CO) 3 (PPh 3 ) 2 ] (5) with oxalic acid. The remaining proton of the Hox − ligand of [Tc(η 2 -oxH)(CO) 2 (PPh 3 ) 2 ] (12) can be removed by NEt 3 , and the ion pair (HNEt 3 )[Tc(η 2 -ox)(CO) 2 (PPh 3 ) 2 ] (13) is formed.

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“…The resulting solutions contain only one paramagnetic species, [TcNF 4 ] – , which gives an intense axially‐symmetric EPR spectrum with well‐resolved ten‐line patterns in the parallel and perpendicular parts (Figure ). The existence of hexacoordinate species such as [TcNF 4 Y] –/2– with F – , H 2 O, or other solvent molecules in trans position to the nitrido ligand is controversially discussed, but at least for aqueous HF solutions no evidence has been found for such species , , ,…”

Section: Resultsmentioning

confidence: 99%

“…With regard to our recent experience with the isolation of [TcF 6 ] 2– and [Tc(NO)F 5 ] 2– salts, where sometimes the selection of an appropriate counterion (or mixtures of such ions) played a crucial role, we started a re‐investigation of the behavior of the nitridofluorides of technetium(VI) in solution and isolated two of the products in crystalline form.…”

Section: Introductionmentioning

confidence: 99%