1. Ring-Size-Modulated Reactivity of Putative Dicobalt-Bridging Nitrides: C−H Activation versus Phosphinimide Formation.
- Author
-
Cui, Peng, Wang, Qiuran, McCollom, Samuel P., Manor, Brian C., Carroll, Patrick J., and Tomson, Neil C.
- Subjects
COBALT compounds ,METAL complexes ,REACTIVITY (Chemistry) ,NITRIDES ,CARBON-hydrogen bonds ,PHOSPHINIMIDES - Abstract
Dicobalt complexes supported by flexible macrocyclic ligands were used to target the generation of the bridging nitrido species [(
n PDI2 )Co2 (μ-N)(PMe3 )2 ]3+ (PDI=2,6-pyridyldiimine; n=2, 3, corresponding to the number of catenated methylene units between imino nitrogen atoms). Depending on the size of the macrocycle and the reaction conditions (solution versus solid-state), the thermolysis of azide precursors yielded bridging phosphinimido [(2 PDI2 )Co2 (μ-NPMe3 )(PMe3 )2 ]3+ , amido [(n PDI2 )Co2 (μ-NH2 )(PMe3 )2 ]3+ ( n=2, 3), and C−H amination [(3 PDI2 *-μ-NH)Co2 (PMe3 )2 ]3+ products. All results are consistent with the initial formation of [(n PDI2 )Co2 (μ-N)(PMe3 )2 ]3+ , followed by 1) PMe3 attack on the nitride, 2) net hydrogen-atom transfer to form N−H bonds, or 3) C−H amination of the alkyl linker of then PDI2 ligand. [ABSTRACT FROM AUTHOR]- Published
- 2017
- Full Text
- View/download PDF