Multinuclear Magnesium Hydride Clusters: Selective Reduction and Catalytic Hydroboration of Pyridines
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https://figshare.com/articles/dataset/Multinuclear_Magnesium_Hydride_Clusters_Selective_Reduction_and_Catalytic_Hydroboration_of_Pyridines/2241721
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资源简介：
Multinuclear
magnesium hydride complexes react with pyridine, forming
1,2- and 1,4-dihydropyridide (DHP) complexes. Reaction of PARA3Mg8H10 with pyridine initially
formed 1,2-DHP and 1,4-DHP product mixtures which converted at 60
°C into PARA-[Mg(1,4-DHP)]2·(pyridine)2 (PARA = [(2,6-iPr2C6H3)NC(Me)C(H)C(Me)N]2-(p-C6H4)). Reaction of [NN-(MgH)2]2 with pyridine gave exclusive formation
of the 1,2-DHP product NN-[Mg(1,2-DHP)]2·(pyridine)2 (NN = [(2,6-iPr2C6H3)NC(Me)CHC(Me)N−]2).
Both products were characterized by crystal structure determinations.
The unusual preference for 1,2-addition is likely caused by secondary
intramolecular interactions based on mutual communication between
the metal coordination geometries: an extended network of C–H···C
π-interactions and π-stacking interactions is found. Whereas PARA3Mg8H10 is hardly active
in magnesium-catalyzed hydroboration of pyridines with pinacolborane,
[NN-(MgH)2]2 shows efficient coupling.
However, the regioselectivity of the stoichiometric reaction is not
translated to the catalytic regime. This result is taken as an indication
for a potential alternative mechanism in which magnesium hydride intermediates
do not play a role but the hydride is transferred from an intermediate
borate complex.
创建时间：
2016-02-16
