TY - JOUR
T1 - Symmetrical and Mixed Tris(acyl)phosphines
T2 - Synthesis, Oxidation and Photochemistry
AU - Wiesner, Tanja
AU - Neshchadin, Dmytro
AU - Glotz, Gabriel
AU - Gfader, Zeno
AU - Schrader, Erik
AU - Christen, Samuel
AU - Fischer, Roland C.
AU - Kelterer, Anne Marie
AU - Gescheidt, Georg
AU - Grützmacher, Hansjörg
AU - Haas, Michael
N1 - Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
PY - 2023/12/1
Y1 - 2023/12/1
N2 - Herein, we present a convenient synthesis for symmetrical and mixed substituted tris(acyl)phosphines (TAPs) starting from red phosphorus. All TAPs exhibit a phosphaalkene-acylphosphine equilibrium, which was investigated in detail by variable-temperature (VT) NMR spectroscopy supported by density-functional theory (DFT) calculations. Depending on the substituents, two phosphaalkene derivatives and ten acylphosphine derivatives could be isolated. NMR spectroscopy and single-crystal X-ray crystallography enabled a clear structural assignment of these compounds. Oxidation of selected TAPs led to the formation of the corresponding tris(acyl)phosphine oxides (TAPOs). Furthermore, their spectroscopic properties as well as their photochemistry was investigated. Especially, the TAPO compounds were evaluated for their suitability as photoinitiators by CIDNP spectroscopy, photobleaching measurements and by storage stability tests.
AB - Herein, we present a convenient synthesis for symmetrical and mixed substituted tris(acyl)phosphines (TAPs) starting from red phosphorus. All TAPs exhibit a phosphaalkene-acylphosphine equilibrium, which was investigated in detail by variable-temperature (VT) NMR spectroscopy supported by density-functional theory (DFT) calculations. Depending on the substituents, two phosphaalkene derivatives and ten acylphosphine derivatives could be isolated. NMR spectroscopy and single-crystal X-ray crystallography enabled a clear structural assignment of these compounds. Oxidation of selected TAPs led to the formation of the corresponding tris(acyl)phosphine oxides (TAPOs). Furthermore, their spectroscopic properties as well as their photochemistry was investigated. Especially, the TAPO compounds were evaluated for their suitability as photoinitiators by CIDNP spectroscopy, photobleaching measurements and by storage stability tests.
KW - acylphosphine oxides
KW - acylphosphines
KW - phosphaalkenes
KW - phosphorus
KW - photochemistry
UR - http://www.scopus.com/inward/record.url?scp=85174593152&partnerID=8YFLogxK
U2 - 10.1002/chem.202302535
DO - 10.1002/chem.202302535
M3 - Article
C2 - 37701996
AN - SCOPUS:85174593152
SN - 0947-6539
VL - 29
JO - Chemistry - a European Journal
JF - Chemistry - a European Journal
IS - 67
M1 - e202302535
ER -