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Theoretical Evidence for the Utilization of Low‐Valent Main‐Group Complexes as Rare‐Synthon Equivalents
Author(s) -
Benedek Zsolt,
Orbán Balázs,
Szilvási Tibor
Publication year - 2017
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.201703636
Subject(s) - phosphinidene , synthon , chemistry , moiety , steric effects , trimethylsilyl , reactivity (psychology) , group (periodic table) , functional group , organic synthesis , medicinal chemistry , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology , polymer
We examine by the means of computational chemistry the ability of two phosphasilenes to transfer the phosphinidene moiety to four double bonded organic functional groups (>C=C<, ‐N=N‐, >C=O, and >C=S) in the presence of different bulky ligands. We show that large bulky groups in the reactants can sterically prohibit the otherwise favored association of reactants and phosphasilenes and instead a new phosphinidene transfer reaction can occur. We find that the transfer reaction mechanism is generally present independent from the functional group and by introducing large enough trimethylsilyl or tert ‐butyl‐dimethylsilyl ligands it can be used to transfer phosphinidene to organic functional groups such as thioformaldehydes or diazenes, respectively. We propose that by exploiting the complex bonding nature of low‐valent main group complexes they can act as synthetic equivalents of hitherto unknown very reactive synthons. We encourage experimentalists to explore the reactivity of their main‐group complexes by varying the size of the bulky substituents on the reactants that can result in new unexpected chemistry.