A novel reactivity of [{Cp*Cr(CO)(3)}(2)(mu,eta(1:1)-P-4)] (Cp*=C5Me5; 1) is reported, which utilizes the selective cleavage of the two P-Cr bonds and subsequently initiates a substituent exchange yielding P-4 butterfly compounds. By means of NMR and IR spectroscopy studies, the successful implementation of 1 to obtain [{Cp ''' Fe(CO)(2)}(2)(mu,eta(1:1)-P-4)] (Cp '''=(C5H2Bu3)-Bu-t; 2) and Cp ''' P-2(4) (3) could be confirmed, by reacting 1 with 2.0 eq. of K[Cp ''' Fe(CO)(2)] or NaCp ''', respectively. Hereby, a quantitative conversion could be detected alongside the formation of 2.0 eq. of the [Cp*Cr(CO)(3)](-) anion. Moreover, various syntheses of novel organometallic and organo-P-4 butterfly compounds were examined and first results show that the generation of different compounds should be possible. However, the isolation and stabilization of these sensitive molecules proves to be a major challenge.