Synthesis and Reactivity of Multinuclear Gold Complexes with (Diphenylphosphanyl)ferrocene and Oxygen Ligands

Au I complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands in their molecules were synthesized, viz . the gold hydroxides [Au(OH)(L‐κ P )] ( 5 ) and [{Au(L‐κ P )} 2 (μ‐OH)][BF 4 ] ( 4 ), and the oxonium cluster [{Au(L‐κ P )} 3 (μ 3 ‐O)][BF 4 ] ( 1 ). In‐situ auration of 1 produced [{Au(L‐κ P )} 4 (μ 4 ‐O)][BF 4 ] 2 ( 2 ), which spontaneously converted into a dimeric tetragold complex featuring bridging phosphanylferrocenyl groups geminally diaurated in position 2 of the ferrocene scaffold. The same complex and its isomer incorporating ferrocene‐1,1′‐diyl bridges resulted similarly from 4 . Upon crystallization, compound 5 underwent a redox reaction, producing a structurally unique, crown‐like, mixed‐valent Au 0 /Au I cluster, [Au 7 (L‐κ P ) 6 ]OH. Compounds 1 and 5 were used to prepare the analogous, N‐bridged complexes, [{Au(L‐κ P )} 3 (μ 3 ‐NFc)][BF 4 ] (Fc=ferrocenyl) and [{Au(L‐κ P )} 4 (μ 4 ‐N)][BF 4 ]. The compounds were structurally characterized and further studied by DFT calculations.