Reaction of the mono-deprotonated derivative of [{Cp(CO)2Mo}2(-PH2)(-H)] (1) leads to the novel complex [{Cp(CO)2Mo}2(-H){3-P(H)Au(PPh3)}] (2). In contrast the reaction of the analogous Cr derivative [{Cp(CO)2Cr}2(-PH2)(-H)] (1a) leads under identical conditions to a planar Au3P3 cluster [{CpCr(CO)2}6(P3Au3)] (3). Both complexes were completely structurally and spectroscopically characterised. Density functional calculations have shown that 3 is characterised by P-Cr-Au multicentre and Cr-P multiple bonding.