Synthesis and Reactivity of Multinuclear Gold Complexes with (Diphenylphosphanyl)ferrocene and Oxygen Ligands.
Jiří SchulzIvana CísařováRóbert GyepesPetr ŠtěpničkaPublished in: Angewandte Chemie (International ed. in English) (2021)
AuI complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands in their molecules were synthesized, viz. the gold hydroxides [Au(OH)(L-κP)] (5) and [{Au(L-κP)}2 (μ-OH)][BF4 ] (4), and the oxonium cluster [{Au(L-κP)}3 (μ3 -O)][BF4 ] (1). In-situ auration of 1 produced [{Au(L-κP)}4 (μ4 -O)][BF4 ]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 Au0 /AuI cluster, [Au7 (L-κP)6 ]OH. Compounds 1 and 5 were used to prepare the analogous, N-bridged complexes, [{Au(L-κP)}3 (μ3 -NFc)][BF4 ] (Fc=ferrocenyl) and [{Au(L-κP)}4 (μ4 -N)][BF4 ]. The compounds were structurally characterized and further studied by DFT calculations.