Evaluation of Tungsten Catalysis among Early Transition Metals for N-Aryl-2,3,4,5-tetraarylpyrrole Synthesis: Modular Access to N-Doped π-Conjugated Material Precursors.
Inorg Chem
; 63(6): 3037-3046, 2024 Feb 12.
Article
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| MEDLINE
| ID: mdl-38300807
ABSTRACT
Low-valent tungsten species generated from WCl6 and N,N'-bis(trimethylsilyl)-2,5-dimethyldihydropyrazine (Si-Me2-DHP) promotes the catalytic formation of N-phenyl-2,3,4,5-tetraarylpyrroles 3aa-ka from diarylacetylenes 1a-k and azobenzene (2a). An initial catalyst activation process is a three-electron reduction of WCl6 with Si-Me2-DHP to afford transient 'WCl3' species. Catalytically active bis(imido)tungsten(VI) species via successive one-electron reduction and NâN bond cleavage of 2a was revealed by isolating W(âNPh)2Cl2(PMe2Ph)2 from imidotungsten(V) trichloride and 2a in the presence of PMe2Ph. The superior catalytic activity of the tungsten catalyst was clarified by a density functional theory study activation energies for the key three steps, [2 + 2]-cycloaddition of WâNPh and diarylacetylene to form (iminoalkylidene)tungsten species, enyne metathesis with second diarylacetylene, and C-N bond formation, are reasonable values for the catalytic reaction at 180 °C. In addition, this tungsten catalyst overcame two distinct deactivation processes α-enediamido formation and aggregation of the low-valent species, both of which were observed for previously developed vanadium and titanium catalysts. We also demonstrated the synthetic utility of pentaarylpyrroles 3aa and 3ba as well as N-(2-bromophenyl)-2,3,4,5-tetraarylpyrrole 3ab by derivatizing their π-conjugated compounds 9aa, 10ba, and 11ab.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Año:
2024
Tipo del documento:
Article
País de afiliación:
Japón
Pais de publicación:
Estados Unidos