Publication | Closed Access
Ring‐Size‐Modulated Reactivity of Putative Dicobalt‐Bridging Nitrides: C−H Activation versus Phosphinimide Formation
49
Citations
45
References
2017
Year
Dicobalt complexes supported by flexible macrocyclic ligands were used to target the generation of the bridging nitrido species [(<sup>n</sup> PDI<sub>2</sub> )Co<sub>2</sub> (μ-N)(PMe<sub>3</sub> )<sub>2</sub> ]<sup>3+</sup> (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 [(<sup>2</sup> PDI<sub>2</sub> )Co<sub>2</sub> (μ-NPMe<sub>3</sub> )(PMe<sub>3</sub> )<sub>2</sub> ]<sup>3+</sup> , amido [(<sup>n</sup> PDI<sub>2</sub> )Co<sub>2</sub> (μ-NH<sub>2</sub> )(PMe<sub>3</sub> )<sub>2</sub> ]<sup>3+</sup> (n=2, 3), and C-H amination [(<sup>3</sup> PDI<sub>2</sub> *-μ-NH)Co<sub>2</sub> (PMe<sub>3</sub> )<sub>2</sub> ]<sup>3+</sup> products. All results are consistent with the initial formation of [(<sup>n</sup> PDI<sub>2</sub> )Co<sub>2</sub> (μ-N)(PMe<sub>3</sub> )<sub>2</sub> ]<sup>3+</sup> , followed by 1) PMe<sub>3</sub> attack on the nitride, 2) net hydrogen-atom transfer to form N-H bonds, or 3) C-H amination of the alkyl linker of the <sup>n</sup> PDI<sub>2</sub> ligand.
| Year | Citations | |
|---|---|---|
Page 1
Page 1