Lewis acidic early transition metals and electron-rich late transition metals can be brought into close proximity by using a phosphinoamide ligand scaffold, resulting in polar metal-metal bonds. The synthesis of a bis(phosphinoamide) zirconium/ cobalt tetrametallic dinitrogen complex has been accomplished, featuring an unprecedented dinitrogen binding mode and extreme N-N bond elongation. The complex features a novel side-on binding of dinitrogen to a late transition metal, which lends support to some models of dinitrogen binding in nitrogenase. The capability of this complex to cleave the dinitrogen bond under catalytic conditions will be discussed.

Synthesis and reactivity of a bis(phosphinoamide) Zr/Co heterobimetallic complex featuring an unprecedented dinitrogen binding mode

ACS Fall 2021

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