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C sp 3 H Bond Activation with Triel Metals: Indium and Gallium Zwitterions through Internal Hydride Abstraction in Rigid Salan Ligands
Author(s) -
Maudoux Nicolas,
Fang Jian,
Roisnel Thierry,
Dorcet Vincent,
Maron Laurent,
Carpentier JeanFrançois,
Sarazin Yann
Publication year - 2014
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.201402358
Subject(s) - chemistry , protonolysis , hydride , moiety , zwitterion , ligand (biochemistry) , medicinal chemistry , methylene , steric effects , stereochemistry , metal , crystallography , molecule , organic chemistry , catalysis , biochemistry , receptor
The hydropyrimidine salan (salan= N , N ′‐dimethyl‐ N , N ′‐bis[(2‐hydroxyphenyl)methylene]‐1,2‐diaminoethane) proteo‐ligands with a rigid backbone {ON^(CH 2 )^NO}H 2 react with M(CH 2 SiMe 3 ) 3 (M=Ga, In) to yield the zwitterions {ON^(CH + )^NO}M − (CH 2 SiMe 3 ) 2 (M=Ga, 2 ; In, 3 ) by abstraction of a hydride from the ligand backbone followed by elimination of dihydrogen. By contrast, with Al 2 Me 6 , the neutral‐at‐metal bimetallic complex [{ON^(CH 2 )^NO}AlMe] 2 ( [1] 2 ) is obtained quantitatively. The formation of indium zwitterions is also observed with sterically more encumbered ligands containing o ‐Me substituents on the phenolic rings, or an N (CHPh) N moiety in the heterocyclic core. Overall, the ease of C sp 3H bond activation follows the order Al≪Ga