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Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement
Author(s) -
Bruce Marlene,
Papke Martin,
Ehlers Andreas W.,
Weber Manuela,
Lentz Dieter,
Mézailles Nicolas,
Slootweg J. Chris,
Müller Christian
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903344
Subject(s) - chemistry , denticity , coordination sphere , ligand (biochemistry) , cycloaddition , photochemistry , coordination complex , derivative (finance) , methane , transition metal , chelation , metal , reaction mechanism , medicinal chemistry , catalysis , organic chemistry , biochemistry , receptor , financial economics , economics
The [4+2] cycloaddition of 2‐(2′‐pyridyl)‐4,6‐diphenyl‐λ 3 ‐phosphinine with the highly reactive dienophile hexafluoro‐2‐butyne has been studied and the first pyridyl‐functionalized 1‐phosphabarrelene was obtained and structurally characterized. Although monodentate CF 3 ‐1‐phosphabarrelenes show only a poor coordination ability, the chelating nature of the novel P,N‐hybrid ligand gives access to various transition‐metal complexes. Upon irradiation with UV light, the pyridyl‐functionalized 1‐phosphabarrelene undergoes a rather selective di‐π‐methane rearrangement in the coordination sphere of the metal center, leading to the formation of a complex based on a hitherto unknown pyridyl‐functionalized 5‐phosphasemibullvalene derivative. DFT calculations provide first insights into the mechanism of this reaction.