Heterocyclic‐2‐thione Derivatives of Silver(I): The Methyl Substituent at N 1 atom of a Imidazoline‐2‐thione/Imidazolidine‐2‐thione Alters a Dimer [Ag 2 (HL) 4 (PPh 3 ) 2 ](NO 3 ) 2 into a Monomer [Ag(HL) 2 (PPh 3 )](NO 3 )

Reactions of silver(I) nitrate with 1,3‐imidazolidine‐2‐thiones (L I ‐NH, L I ‐NMe), 1,3‐imidazoline‐2‐thiones (L II ‐NH, L II ‐NMe), and that of silver(I) acetate with thiazolidine‐2‐thione (L III ‐NH), or benz‐imidazoline‐2‐thione (L IV ‐NH) and triphenylphosphine (PPh 3 ) as co‐ligand (1:2:2 molar ratios) in acetonitrile, acetonitrile‐methanol, or acetonitrile‐acetone mixtures have yielded mono‐ and dinuclear complexes of stoichiometry: [Ag 2 {µ‐(L I ‐NH‐ S )} 2 (L I ‐NH‐ S ) 2 (PPh 3 ) 2 ](NO 3 ) 2 · 2CH 3 OH ( 1 ), [Ag(L I ‐NMe‐ S ) 2 (PPh 3 )](NO 3 ) ( 2 ), [Ag 2 {µ‐(L II ‐NH‐ S )} 2 (L II ‐NH‐ S ) 2 (PPh 3 ) 2 ](NO 3 ) 2 · 2CH 3 OH ( 3 ), [Ag(L II ‐NMe‐ S ) 2 (PPh 3 )](NO 3 ) ( 4 ), [Ag(L III ‐NH‐ S )(L III ‐N‐ S )(PPh 3 ) 2 ] ( 5 ), and [Ag(L IV ‐NH‐ S ) 2 (PPh 3 ) 2 ](OAc) · H 2 O ( 6 ). In complex 5 , one thio ligand is anionic (L III ‐N – ), whereas all other complexes have neutral thio ligands bonded to Ag I ion. The complexes were characterized using elemental analysis, IR, 1 H and 31 P NMR spectroscopy and single crystal X‐ray crystallography. It is interesting to note that L I ‐NH and L II ‐NH ligands formed dinuclear complexes 1 and 3 with four‐coordination around each metal center, whereas the presence of a methyl group at one nitrogen atom (i.e. L I ‐NMe and L II ‐NMe) yielded mononuclear complexes 2 and 4 with three‐coordination around each metal center. The ligands L III ‐NH and L IV ‐NH behaved differently.