TY - JOUR
T1 - Evaluation of Tungsten Catalysis among Early Transition Metals for N-Aryl-2,3,4,5-tetraarylpyrrole Synthesis
T2 - Modular Access to N-Doped π-Conjugated Material Precursors
AU - Tsurugi, Hayato
AU - Akiyama, Takuya
AU - Frye, Connor W.
AU - Kakiuchi, Yuya
AU - Mashima, Kazushi
AU - Tonks, Ian A.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/2/12
Y1 - 2024/2/12
N2 - 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 N═N bond cleavage of 2a was revealed by isolating W(═NPh)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 W═NPh 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.
AB - 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 N═N bond cleavage of 2a was revealed by isolating W(═NPh)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 W═NPh 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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U2 - 10.1021/acs.inorgchem.3c03858
DO - 10.1021/acs.inorgchem.3c03858
M3 - Article
C2 - 38300807
AN - SCOPUS:85184819767
SN - 0020-1669
VL - 63
SP - 3037
EP - 3046
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 6
ER -