Gold(I) {2}‐Metallacoronates derived from a Catechol‐scaffolding Aroylbis(N,N‐diethylthiourea): Syntheses and Structures

One‐pot reactions of catechol‐scaffolding aroylbis( N , N ‐diethylthiourea) H 2 L cat and mixtures of lanthanide nitrates Ln(NO 3 ) 3 (Ln 3+ =La 3+ , Nd 3+ or Yb 3+ ) or indium(III) chloride InCl 3 and [Au(tht)Cl] in methanol in the presence of the supporting base Et 3 N result in gold(I) {2}‐metallacoronates. Depending on radii of the trivalent metal ions, the corresponding complexes are separated either in the neutral form with the composition {(NO 3 ‐κ 2 ‐ O , O’ )Ln⊂[Au 2 (L cat ) 2 ]} in the cases of La 3+ and Nd 3+ or as the ‘ion‐pair’ {Yb⊂[Au 2 (L cat ) 2 ]} + (NO 3 ) − for the Yb(III) compound. The cationic complexes can be isolated in higher yields as the PF 6 − salts {M⊂[Au 2 (L cat ) 2 ]} + (PF 6 ) − (M 3+ =Yb 3+ or In 3+ ) by treatment of reaction mixtures with ( n ‐Bu 4 N)(PF 6 ).