The formation and cleavage of chemical bonds in catalytic reactions relies on accessible two-electron redox processes that are often challenging for base metals such as first row and early transition metals. Metal-metal cooperativity in early/late heterobimetallic complexes provides a potential solution to this challenge both by facilitating redox processes and enabling heterolytic bond cleavage processes that are not possible with monometallic compounds. In this context, tris(phosphinoamide) early/late heterobimetallic frameworks have been shown to support metal-metal multiple bonds and facilitate redox processes across a broad range of varying metal-metal combinations and the resulting complexes have been shown to readily cleave polar C=O bonds and catalyze organic transformations. Building upon these findings, more coordinatively unsaturated bis(phosphinoamide)-supported bimetallics have been shown to have similar metal-metal bonding but with significantly enhanced reactivity towards a wider range of bond activation processes. For example, a Zr/Co bis(phosphinoamide) complex readily activates H<sub>2</sub> across the metal-metal bond and this reactivity has been harnessed for the catalytic hydrogenation of unsaturated hydrocarbons. The most recent discoveries of bond activation processes and catalytic applications of early/late heterobimetallic complexes will be discussed.<br/>

Bond activation and catalysis facilitated by early/late metal-metal cooperativity

ACS Fall 2020 Virtual Meeting

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