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Coordination Versatility and Amide Shift in Mononuclear Fe II Complexes with the Asymmetrical Tripod [(6‐Bromo‐2‐pyridyl)methyl][(6‐pivaloylamido‐2‐pyridyl)methyl](2‐pyridylmethyl)amine (BrMPPA)
Author(s) -
Thibon Aurore,
KarmazinBrelot Lydia,
Mandon Dominique
Publication year - 2013
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.201201284
Subject(s) - chemistry , tripod (photography) , steric effects , amide , hexacoordinate , ligand (biochemistry) , amine gas treating , coordination sphere , medicinal chemistry , stereochemistry , pyridine , coordination complex , crystallography , metal , crystal structure , organic chemistry , biochemistry , physics , receptor , silicon , optics
We report in this communication the preparation of the BrMPPA ligand, a new tris(2‐pyridylmethyl)amine‐type tripod in which di‐α‐substitution by an amido group and a bromine atom, respectively, provide functionality and sterically induced ligand flexibility. The coordination versatility of this tripod is evidenced by the complete characterization of two dichlorido and di‐triflato Fe II complexes in the solid state and in solution. The new tripod can potentially act as a κ 5 ligand with coordination of the carbonyl group of the amide function. This is true when there is little steric hindrance at the coordination site. With bulky chlorido ligands, however, decoordination occurs, and the tripod becomes a κ 4 chelate. In this case, a state‐dependent coordination mode is reported: A dangling pyridyl group is observed in solution, whereas the carbonyl group is noncoordinated in the solid state, the three pyridine groups remaining bound.