White phosphorus, yellow arsenic, and AsP₃ have been successfully activated by a complex with a Cr-Cr quintuple bond in one step leading to the formation of rare terminally bound cyclo-P₄ ^2-, cyclo-As₄^2-, and cyclo-AsP₃ units. The subsequent reaction with an excess of [W(CO)₅(thf)] leads to the coordination of one {W(CO)₅} fragment in the thermodynamically most stable form according to DFT calculations.