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Exploiting the Versatility of Phosphinobenzylsilanes for the Stabilization of 14‐Electron Rhodium(III) and Iridium(III) Complexes
Author(s) -
CoronaGonzález María Vicky,
ZamoraMoreno Julio,
MuñozHernández Miguel A.,
Vendier Laure,
SaboEtienne Sylviane,
MontielPalma Virginia
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900107
Subject(s) - chemistry , rhodium , iridium , phosphine , silicon , agostic interaction , isopropyl , valence electron , ligand (biochemistry) , electron donor , valence (chemistry) , stereochemistry , crystallography , electron , medicinal chemistry , organic chemistry , catalysis , biochemistry , physics , receptor , quantum mechanics , metal
Incorporating pendant silicon functionalities into phosphine ligands enables to profit from the strong σ‐electron donor and trans influence properties of Si while enhancing the coordination ability of the ligand. Herein, we show that the introduction of bulky sigma donor substituents on the Si atoms and modulation of the number of Si–H functional groups in a series of phosphinobenzylsilanes allow either the stabilization of rare highly unsaturated 14‐electron rhodium(III) and iridium(III) species devoid of agostic interactions or the access to mixed‐valence M I –M III complexes. Our findings using isopropyl‐substituted silicon are markedly different from those obtained when employing the methyl‐substituted Si series.