The potassium graphite reduction of L:PCl3 leads to the formation of carbene-stabilized diphosphorus molecules, L:P-P:L, 1 (L: = :C{N (2,6-(Pr2C6H3)-C-i)CH}(2)) and 2 (L: = :C{N(2,4,6-Me3C6H2)CH}2), respectively. The nature of the bonding in 1 and 2 was delineated by DFT computations.