Activation of Di-tert-butyldiphosphatetrahedrane: Access to (tBuCP)n (n=2, 4) Ligand Frameworks by P-C Bond Cleavage

The first mixed phosphatetrahedranes were reported only recently and their reactivity is virtually unexplored. Herein, we present a reactivity study on di-tert-butyldiphosphatetrahedrane (1), which is the dimer of tert-butylphosphaalkyne. The (tBuCP)(2) tetrahedron is activated selectively by N-heterocyclic carbene (NHC) nickel(I) and nickel(0) complexes, resulting in novel complexes featuring diverse (tBuCP)(n)-frameworks (n=2, 4). Release of the (tBuCP)(4) framework from one of the complexes was achieved by addition of CO gas. Furthermore, 1 can be used as a source for P-2 units by elimination of di-tert-butylacetylene in the coordination sphere of nickel.

Automated summary

The reactivity of di-tert-butyldiphosphatetrahedrane was studied, showing selective activation by N-heterocyclic carbene nickel(I) and nickel(0) complexes to form novel complexes. Furthermore, release of the tetrahedral framework was achieved by addition of CO gas.