The Staudinger reaction of unprotected azido-peptides with silylated phosphinic acids and esters on the solid support offers a straightforward acid-free entry to different phosphonamidate peptide esters or acids under mild conditions in high purity and yield.
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Cross-bridged cyclam derivatives with bis(phosphinate) and phosphinate-phosphonate pendant arms (cb-BPC) as chelators for copper radioisotopes.
Org Biomol Chem
January 2025
Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Prague, Czech Republic.
Copper radioisotopes can be used for imaging as well as for therapy and, thus, can form ideal theranostic pairs. The Cu(II) complexes of cross-bridged cyclam (cb-cyclam) derivatives are considered to be highly stable . However, the complexes are mostly formed under harsh conditions not compatible with sensitive biomolecules.
View Article and Find Full Text PDFSynthesis of heteroleptic bis-phosphine bis-NHC iron (0) complexes: a strategy to enhance small molecule activation.
Chem Commun (Camb)
November 2024
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109, USA.
We report the synthesis of heteroleptic iron complexes supported by both a bis-phosphine ligand (depe) and a bis-NHC ligand. The mixed ligand sets provide access to iron (0) adducts of N and CO that are highly activated, in comparison to homoleptic ( Fe(depe)L) variants. Computational and experimental studies revealed the mixed ligand set distorts the geometric and electronic structure to yield an unusually basic iron.
View Article and Find Full Text PDFDinitrogen silylation catalyzed by silylene cobalt(I) and silylene iron(I) chlorides.
Dalton Trans
October 2024
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250100 Jinan, People's Republic of China.
In this contribution, Co(PMe)Cl (1), bis(silylene) cobalt chlorides Co(LSi:)(PMe)Cl (LSi: = {PhC(NBu)}SiCl (2); {-CHCHC(NBu)}SiCl (3); and {-BuCHC(NBu)}SiCl (4)) and bis(silylene) iron chlorides Fe(LSi:)(PMe)Cl (LSi: = {PhC(NBu)}SiCl (5); {-CHCHC(NBu)}SiCl (6); {-BuCHC(NBu)}SiCl (7) and Fe(PMe)Cl (8)) were synthesized to study the effects of different metals and silylene ligands on the catalytic activity of complexes 1-8 in dinitrogen silylation reaction. The experimental results indicate that there is no substantial difference in catalytic activity between the phosphine cobalt complex 1 and the silylene cobalt chlorides 2-4 although the cobalt silylene complex 2 has slightly better catalytic activity than complexes 1, 3 and 4 in the dinitrogen silylation. Silylene iron complexes 5-7 are more active than the phosphine iron complex 8.
View Article and Find Full Text PDFCationic Bis(hydrosilane)-Coinage-Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer-Sphere C=O Hydrosilylation Not Involving Metal Hydrides.
Angew Chem Int Ed Engl
September 2024
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
The preparation of cationic bis(hydrosilane)-coinage-metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BAr ] is described. Unlike previously reported hydrosilane-stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate (ortho-silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X-ray diffraction analysis, revealing that both Si-H bonds are activated by the Lewis acidic cationic metal center.
View Article and Find Full Text PDFRecent Advances on the Chemistry of Transition Metal Complexes with Monoanionic Bidentate Silyl Ligands.
Chempluschem
September 2024
Departamento de Química Inorgánica - Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza -CSIC, Facultad de Ciencias, Plaza de San Francisco, 50009, Zaragoza, Spain.
The chemistry of transition-metal (TM) complexes with monoanionic bidentate (κ-L,Si) silyl ligands has considerably grown in recent years. This work summarizes the advances in the chemistry of TM-(κ-L,Si) complexes (L=N-heterocycle, phosphine, N-heterocyclic carbene, thioether, ester, silylether or tetrylene). The most common synthetic method has been the oxidative addition of the Si-H bond to the metal center assisted by the coordination of L.
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