[{TcI(NO)(LOMe)(PPh3)Cl}2Ag](PF6) and [TcII(NO)(LOMe)(PPh3)Cl](PF6): Two Unusual Technetium Complexes with a “Kläui‐type” Ligand

Jungfer, Maximilian Roca; Ernst, Moritz Johannes; Hagenbach, Adelheid; Abram, Ulrich

doi:10.1002/zaac.202100316

Cited by 5 publications

(2 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The proton spectrum clearly shows the expected narrow signals for the diamagnetic d 6 complex, while the lines observed for the hetero nuclei 15 N and 31 P are remarkably broadened. Similar observations have been made before for other (non-symmetric) phosphine complexes of technetium(I), -(III), and -(V), and have been assigned to scalar couplings of the 31 P nucleus with the large quadrupole moment of 99 Tc [ 34 , 59 , 61 , 62 , 81 , 97 , 98 , 99 ]. The resulting line broadenings make the detection of reasonable 31 P NMR spectra in some cases almost impossible (see also Figure 4 ).…”

Section: Resultssupporting

confidence: 83%

“…Thus, they can be understood formally as NO + units. This is in perfect agreement with all other hitherto structurally characterized nitrosyl compounds of technetium [32][33][34][35]66,[70][71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86] and the short N10-O10 bonds reflect the π-backdonation discussed above.…”

Section: Synthesis and Reactions Of [Tc(no)(cp)(pph3)(ncch3)] + Saltssupporting

confidence: 91%

See 1 more Smart Citation

[Tc(NO)(Cp)(PPh3)Cl] and [Tc(NO)(Cp)(PPh3)(NCCH3)](PF6), and Their Reactions with Pyridine and Chalcogen Donors

Ernst,

Abdulkader,

Hagenbach

et al. 2024

Molecules

View full text Add to dashboard Cite

Reactions of the technetium(I) nitrosyl complex [Tc(NO)(Cp)(PPh3)Cl] with triphenylphosphine chalcogenides EPPh3 (E = O, S, Se), and Ag(PF6) in a CH2Cl2/MeOH mixture (v/v, 2/1) result in an exchange of the chlorido ligand and the formation of [Tc(NO)(Cp)(PPh3)(EPPh3)](PF6) compounds. The cationic acetonitrile complex [Tc(NO)(Cp)(PPh3)(NCCH3)]+ is formed when the reaction is conducted in NCCH3 without additional ligands. During the isolation of the corresponding PF6− salt a gradual decomposition of the anion was detected in the solvent mixture applied. The yields and the purity of the product increase when the BF4− salt is used instead. The acetonitrile ligand is bound remarkably strongly to technetium and exchange reactions readily proceed only with strong donors, such as pyridine or ligands with ‘soft’ donor atoms, such as the thioether thioxane. Substitutions on the cyclopentadienyl ring do not significantly influence the ligand exchange behavior of the starting material. 99Tc NMR spectroscopy is a valuable tool for the evaluation of reactions of the complexes of the present study. The extremely large chemical shift range of this method allows the ready detection of corresponding ligand exchange reactions. The observed 99Tc chemical shifts depend on the donor properties of the ligands. DFT calculations support the discussions about the experimental results and provide explanations for some of the unusual findings.

show abstract

Section: Resultssupporting

confidence: 83%

Section: Synthesis and Reactions Of [Tc(no)(cp)(pph3)(ncch3)] + Saltssupporting

confidence: 91%

[Tc(NO)(Cp)(PPh3)Cl] and [Tc(NO)(Cp)(PPh3)(NCCH3)](PF6), and Their Reactions with Pyridine and Chalcogen Donors

Ernst,

Abdulkader,

Hagenbach

et al. 2024

Molecules

View full text Add to dashboard Cite

show abstract

Structural organometallic chemistry of technetium-99

Roca Jungfer,

Besmer

2024

Advances in Organometallic Chemistry

View full text Add to dashboard Cite

Pivotal role of 99Tc NMR spectroscopy in solid-state and molecular chemistry

Kuznetsov,

Poineau,

German

et al. 2024

Commun Chem

View full text Add to dashboard Cite

The radioelement Technetium (element 43) pertains to various domains including the nuclear enterprise (i.e., spent nuclear fuel (SNF) reprocessing and nuclear waste remediation) and nuclear medicine (i.e., development of new imaging agents) as well as to the fundamental science of transition metals (i.e., chemical trends in catalytic properties). One method that can provide critical information to improve knowledge in these domains is 99 Tc nuclear magnetic resonance (NMR) spectroscopy. The review, presented here, summarizes the pivotal role of 99 Tc NMR spectroscopy over the past two decades and presents prospects of the method to tackle challenges in Tc chemistry.

show abstract

[{Tc^I(NO)(L^OMe)(PPh₃)Cl}₂Ag](PF₆) and [Tc^II(NO)(L^OMe)(PPh₃)Cl](PF₆): Two Unusual Technetium Complexes with a “Kläui‐type” Ligand

Cited by 5 publications

References 38 publications

[Tc(NO)(Cp)(PPh3)Cl] and [Tc(NO)(Cp)(PPh3)(NCCH3)](PF6), and Their Reactions with Pyridine and Chalcogen Donors

[Tc(NO)(Cp)(PPh3)Cl] and [Tc(NO)(Cp)(PPh3)(NCCH3)](PF6), and Their Reactions with Pyridine and Chalcogen Donors

Structural organometallic chemistry of technetium-99

Pivotal role of 99Tc NMR spectroscopy in solid-state and molecular chemistry

Contact Info

Product

Resources

About