An Unusual Bonding Situation in a Novel Au I ‐Phosphido Complex with a Planar Au 3 P 3 Framework

Reaction of the mono‐deprotonated derivative of [{Cp(CO) 2 Mo} 2 (μ‐PH 2 )(μ‐H)] ( 1 ) leads to the novel complex [{Cp(CO) 2 Mo} 2 (μ‐H){μ 3 ‐P(H)Au(PPh 3 )}] ( 2 ). In contrast the reaction of the analogous Cr derivative [{Cp(CO) 2 Cr} 2 (μ‐PH 2 )(μ‐H)] ( 1a ) leads under identical conditions to a planar Au 3 P 3 cluster [{CpCr(CO) 2 } 6 (P 3 Au 3 )] ( 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)