Open AccessAn Alkali Metal-Capped Cerium(IV) Imido Complex
Author(s) -
Lukman A. Solola,
Alexander V. Zabula,
Walter L. Dorfner,
Brian C. Manor,
Patrick J. Carroll,
Eric J. Schelter
Publication year - 2016
Publication title -
journal of the american chemical society
Language(s) - Uncategorized
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.6b03293
Subject(s) - chemistry , lanthanide , ligand (biochemistry) , cerium , steric effects , alkali metal , crystallography , metal , valence (chemistry) , moiety , inorganic chemistry , stereochemistry , ion , organic chemistry , biochemistry , receptor
Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å.