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Transition‐Metal‐Like Reversible Cycloadditions of [ t BuSP‐W(CO) 5 ] with Alkenes and Alkynes
Author(s) -
Wang Min,
Xu Yang,
Wei Donghui,
Tian Rongqiang,
Duan Zheng,
Mathey François
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.201902948
Subject(s) - lone pair , homo/lumo , chemistry , methanol , phenanthrene , transition metal , metal , sulfur , medicinal chemistry , dissociation (chemistry) , bond dissociation energy , crystallography , stereochemistry , photochemistry , molecule , organic chemistry , catalysis
tert ‐Butylthiophosphinidene complex [ t BuSP‐W(CO) 5 ] was generated by dissociation of 1‐( tert ‐butylthio)phosphirane–W(CO) 5 complex under mild conditions. The formation of transient [ t BuSP‐W(CO) 5 ] was indicated by trapping reactions with 2,3‐dimethyl‐1,3‐butadiene, alkynes, phenanthrene‐9,10‐dione, and methanol. The LUMO of [MeSP‐W(CO) 5 ] is significantly lower in energy than those of [Me 2 NP‐W(CO) 5 ], [MeOP‐W(CO) 5 ], and [Me 2 PP‐W(CO) 5 ]. The HOMO of [MeSP‐W(CO) 5 ] contains a significant contribution from the in‐plane lone pair of P and the LUMO shows a typical π * characteristic. Since stabilized by sulfur lone pair and coordinated by W(CO) 5 , [ t BuSP‐W(CO) 5 ] undergoes facile and reversible cycloadditions with alkenes and alkynes.