The core of the matter - arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1'-ferrocenylene)arene gold(I) complexes.

Changing the aromatic core of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes has profound effects on their coordination behaviour towards gold(i). Depending on the arene (s-triazine, benzene, or trifluorobenzene), four different coordination modes can be distinguished and their preference has been rationalised using computational methods. The corresponding 1 : 1 ligand-to-metal complexes, studied by variable-temperature NMR spectroscopy, revealed fluctional behaviour in solution. Given the presence of up to three or six ferrocenylene spacers per complex, their electrochemistry was investigated. The redox-responsive nature of the complexes can be advantageously exploited in the catalytic ring-closing isomerisation of N-(2-propyn-1-yl)benzamide, where the benzene-based 2 : 3 ligand-to-metal complex has been shown to display multiple activity states depending on the degree of (reversible) oxidation in a preliminary trial.