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Nucleophilic Reactions of Osmanaphthalynes with PMe 3 and H 2 O
Author(s) -
Zhang MingXing,
Lin Lu,
Yang Xiaofei,
Yin Jun,
Zhu Jun,
Liu Sheng Hua
Publication year - 2021
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.202100176
Subject(s) - trimethylphosphine , nucleophile , chemistry , ligand (biochemistry) , density functional theory , nuclear magnetic resonance spectroscopy , medicinal chemistry , nucleophilic addition , computational chemistry , stereochemistry , crystallography , catalysis , organic chemistry , crystal structure , receptor , biochemistry
Members of a new class of complexes, 2 (CF 3 ), 2 (H), 2 (Br), 2 (I), and 2 (OCH 3 ), have been synthesized in a one‐pot method involving the treatment of osmanaphthalynes bearing corresponding substituents ( 1 (CF 3 ), 1 (H), 1 (Br), 1 (I), and 1 (OCH 3 )) with trimethylphosphine (PMe 3 ) and water. The main reaction process involves two steps, namely a ligand‐exchange with trimethylphosphine and nucleophilic addition of water to the Os≡C bond of the osmanaphthalyne. The substituents have a significant influence on the rate of the reaction, as befits a nucleophilic addition. Fortunately, the key intermediate [ 1 (OCH 3 )]′ could be successfully captured, and the detailed reaction mechanism has been explored with the aid of density functional theory (DFT) calculations, which were in excellent agreement with the experimental findings. All of the target complexes have been fully characterized by 1 H, 31 P{ 1 H}, and 13 C{ 1 H} NMR spectroscopy, high‐resolution mass spectrometry, and elemental analysis.