| Abstract: | A series of dicarbene‐bridged metallacycles [Ag2( 1 )2](PF6)2, [Ag2( 2 )2](BF4)2, [Ag2( 3 )2](PF6)2, [Ag2( 7 )2](BF4)2, [Ag2( 8 )2](BF4)2 and [Ag2( 11 )2](PF6)2 were obtained in high yields via the reactions of 1,2,4‐triazole‐, 1,2,3‐triazole‐ and imidazo[1,5‐a]pyridine‐based ligands with Ag2O in CH3CN. The C=C double bonds in all of the newly synthesized metallacycles went through [2 + 2] photodimerization under UV irradiation condition (λ = 365 nm, T = 298 K) yielding the dinuclear rctt‐cyclobutane‐silver(I) complexes [Ag2( 4 )](PF6)2, [Ag2( 5 )](BF4)2, [Ag2( 6 )](PF6)2, [Ag2( 9 )](BF4)2, [Ag2( 10 )](BF4)2 and [Ag2( 12 )](PF6)2, respectively with quantitative yields. Treatment of the these cyclobutane‐bridged silver(I) complexes with NH4Cl resulted in the exclusive formation of cyclobutane derivatives after removal of the silver(I) metal ions. |
