Silver(i) complexes containing heteroleptic diorganochalcogen(ii) ligands

The reaction of 4-[(CH2O)(2)CH]C6H4Br with n-BuLi, followed by the insertion of the chalcogen (S or Se) and in situ reaction with n-BuBr, has afforded the formation of (n-Bu){4-[(CH2O)(2)CH]C6H4}E [E = Se (1), S (2)]. Deprotection of the formyl groups in 1 and 2 afforded (n-Bu)[4-(CHO)C6H4]E [E = Se (3), S (4)], which were further used for the preparation of (n-Bu)[4-{2-C6H5-(4H)-oxazol-5-one}C6H4]E [E = Se (5), S (6)]. Compounds 3, 5 and 6 were found to be useful ligands for the silver(i) complexes [Ag{(n-Bu)[4-(OCH)C6H4]Se}][OTf] (7) (OTf = CF3SO3) and [Ag{(n-Bu)[4-{2-C6H5-(4H)-oxazol-5-one}C6H4]E}]X [X = OTf, E = Se (8), S (9); X = PF6, E = Se (10), S (11)]. For the identification and characterization of the compounds, multinuclear NMR (H-1, C-13{H-1}, F-19{H-1}, P-31{H-1}, Se-77{H-1}) spectroscopy, UV-Vis spectroscopy, IR spectroscopy, elemental analysis, molar conductivity measurements and mass spectrometry were used, when appropriate. The crystal structures of 5, 6 and 9 were determined by single-crystal X-ray diffraction. The formation of a 1D coordination polymer, [Ag-2(OTf)(2){(n-Bu)[4-{2-C6H5-(4H)-oxazol-5-one}C6H4]S}(2)](n), with a dinuclear core, was observed in 9.

Automated summary

The reaction of 4-[(CH2O)(2)CH]C6H4Br with n-BuLi, followed by the insertion of the chalcogen (S or Se) and in situ reaction with n-BuBr, has led to the formation of (n-Bu){4-[(CH2O)(2)CH]C6H4}E [E = Se (1), S (2)]. Deprotection of the formyl groups in 1 and 2 has resulted in (n-Bu)[4-(CHO)C6H4]E [E = Se (3), S (4)], which were further used for the preparation of (n-Bu)[4-{2-C6H5-(4H)-oxazol-5-one}C6H4]E [E = Se (5), S (6)].