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Synthesis and Ligand Modification Chemistry of a Molybdenum Dinitrogen Complex: Redox and Chemical Activity of a Bis(imino)pyridine Ligand
Author(s) -
Margulieux Grant W.,
Turner Zoë R.,
Chirik Paul J.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408725
Subject(s) - chemistry , molybdenum , pyridine , ligand (biochemistry) , bridging ligand , medicinal chemistry , redox , ammonia , bioinorganic chemistry , chelation , stereochemistry , metal , inorganic chemistry , organic chemistry , receptor , biochemistry
The bis(imino)pyridine 2,6‐(2,6‐ i Pr 2 ‐C 6 H 3 NCPh) 2 ‐C 5 H 3 N ( i Pr BPDI) molybdenum dinitrogen complex, [{( i Pr BPDI)Mo(N 2 )} 2 (μ 2 ,η 1 ,η 1 ‐N 2 )] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N 2 ligands. Addition of ammonia resulted in sequential NH bond activations, thus forming bridging parent imido (μ‐NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal–ligand cooperativity in NH 3 oxidation.