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1. Structural and Redox Variations in Technetium Complexes Supported by m -Terphenyl Isocyanides

   https://doi.org/10.1021/acs.organomet.0c00238  

   Claude, Guilhem; Salsi, Federico; Hagenbach, Adelheid; Gembicky, Milan; Neville, Michael; Chan, Chinglin; Figueroa, Joshua S.; Abram, Ulrich (June 2020, Organometallics)
2. Insertions of Isocyanides in Diamidoamine Rhenium(III) Complexes

   https://doi.org/10.1021/acs.organomet.4c00338  

   Pauly, Liana; Adegboyega, Abdullahi K; Brown, Caleb A; Pérez, Damaris E; Ison, Elon A (December 2024, Organometallics)
3. A closed-shell monomeric rhenium(1−) anion provided by m -terphenyl isocyanide ligation

   https://doi.org/10.1039/d0cc03043k  

   Salsi, Federico; Neville, Michael; Drance, Myles; Hagenbach, Adelheid; Chan, Chinglin; Figueroa, Joshua S.; Abram, Ulrich (January 2020, Chemical Communications)

   The mixed isocyanide/carbonyl complexes cis - and trans -[Re(CO) 3 Br(CNAr Dipp2 ) 2 ] (Ar Dipp2 = 2,6-(2,6-(i-Pr) 2 C 6 H 3 ) 2 C 6 H 3 ) can be synthesized from reactions of [Re(CO) 5 Br] and CNAr Dipp2 depending on the conditions applied. Reduction of the neutral Re( i ) species gives the monoanionic complex [Re(CO) 3 (CNAr Dipp2 ) 2 ] − or the neutral [Re(CO) 3 (CNAr Dipp2 ) 2 ], which contain rhenium in the formal oxidation states “−1” and “0”, respectively. 

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4. The Chemistry of Phenylimidotechnetium(V) Complexes with Isocyanides: Steric and Electronic Factors

   https://doi.org/10.3390/molecules27238546  

   Claude, Guilhem; Zeh, Laura; Roca Jungfer, Maximilian; Hagenbach, Adelheid; Figueroa, Joshua S.; Abram, Ulrich (December 2022, Molecules)

   Organometallic approaches are of ongoing interest for the development of novel functional 99mTc radiopharmaceuticals, while the basic organotechnetium chemistry seems frequently to be little explored. Thus, structural and reactivity studies with the long-lived isotope 99Tc are of permanent interest as the foundation for further progress in the related radiopharmaceutical research with this artificial element. Particularly the knowledge about the organometallic chemistry of high-valent technetium compounds is scarcely developed. Here, phenylimido complexes of technetium(V) with different isocyanides are introduced. They have been synthesized by ligand-exchange procedures starting from [Tc(NPh)Cl3(PPh3)2]. Different reactivity patterns and products have been obtained depending on the steric and electronic properties of the individual ligands. This involves the formation of 1:1 and 1:2 exchange products of Tc(V) with the general formulae [Tc(NPh)Cl3(PPh3)(isocyanide)], cis- or trans-[Tc(NPh)Cl3(isocyanide)2], but also the reduction in the metal and the formation of cationic technetium(I) complex of the formula [Tc(isocyanide)6]+ when p-fluorophenyl isocyanide is used. The products have been studied by single-crystal X-ray diffraction and spectroscopic methods, including IR and multinuclear NMR spectroscopy. DFT calculations on the different isocyanides allow the prediction of their reactivity towards electron-rich and electron-deficient metal centers by means of the empirical SADAP parameter, which has been derived from the potential energy surface of the electron density on their potentially coordinating carbon atoms. 

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5. A Complete Triad of Zero‐Valent 17‐Electron Monoradicals of Group 7 Elements Stabilized by m ‐Terphenyl Isocyanides

   https://doi.org/10.1002/anie.202300254  

   Salsi, Federico; Wang, Shuai; Teutloff, Christian; Busse, Marvin; Neville, Michael L.; Hagenbach, Adelheid; Bittl, Robert; Figueroa, Joshua S.; Abram, Ulrich (April 2023, Angewandte Chemie International Edition)

   Abstract The first consistent series of mononuclear 17‐electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X‐ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M⁰(CO)(CNp‐F‐Ar^DArF2)₄] (M=Mn, Tc, Re; Ar^DArF2=2,6‐(3,5‐(CF₃)₂C₆H₃)₂C₆H₂F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen‐solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large⁹⁹Tc and^185,187Re hyperfine interactions for one component. High‐field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex. 

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