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Formation and Reactivity of a Molecular Magnesium Hydride with a Terminal MgH Bond
Author(s) -
Schnitzler Silvia,
Spaniol Thomas P.,
Maron Laurent,
Okuda Jun
Publication year - 2015
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.201502232
Subject(s) - chemistry , adduct , ligand (biochemistry) , hydride , magnesium , medicinal chemistry , reactivity (psychology) , derivative (finance) , pyridine , magnesium hydride , acetylide , silylation , hydrogen bond , stereochemistry , molecule , organic chemistry , metal , catalysis , medicine , biochemistry , receptor , alternative medicine , pathology , financial economics , economics
A complex featuring a terminal magnesium hydride bond supported by an NNNN macrocyclic ligand, [Mg{Me 3 TACD ⋅ Al( i Bu) 3 }H] ( 3 ), was formed from its labile Al( i Bu) 3 adduct. Use of Al( i Bu) 3 to block the amido nitrogen of the NNNN macrocyclic ligand was essential to prevent aggregation. The structurally characterized compound 3 reacted with BH 3 to give the BH 4 derivative, whereas Me 3 SiCCH and PhSiH 3 led to the corresponding acetylide and silyl derivative under H 2 elimination. Pyridine is inserted into the MgH bond to give selectively the 1,4‐dihydropyridinate.