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Updated: Nov 25, 2025
Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Synthesis and Reactivity of Multinuclear Gold Complexes with (Diphenylphosphanyl)ferrocene and Oxygen Ligands
Jiří Schulz1, Ivana Císařová1, Róbert Gyepes1
1Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague, Czech Republic.
Abstract:
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.
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