Hemilabile silver( i ) complexes containing pyridyl chalcogenolate (S, Se) ligands and their utility as molecular precursors for silver chalcogenides

• Published in: CrystEngComm 2015-01, Vol.17 (23), p.4367-4376
• Main Authors: Kole, Goutam Kumar, Vivekananda, K. V., Kumar, Mukesh, Ganguly, Rakesh, Dey, Sandip, Jain, Vimal K.
• Format: Article
• Language: English
• Subjects: Chalcogenides; Diffraction; Ligands; Methyl alcohol; Molecular structure; Precursors; Silver; Utilities
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/C5CE00626K

A series of silver triphenylphosphine complexes containing pyridyl chacogenolate (S, Se) ligands has been synthesized by employing [AgCl(PPh 3 ) 3 ] and [Ag 2 (μ-Cl) 2 (PPh 3 ) 4 ]. The complexes [Ag(S-4-pyH 0.5 ) 2 (PPh 3 ) 2 ] ( 1 ) and [Ag 2 (μ-S-4-py) 2 (PPh 3 ) 4 ] ( 2 ) were obtained by the reactions of [Ag 2 (μ-Cl) 2 (PPh 3 ) 4 ] with 4-pySH in the presence of Et 3 N and NaOH, respectively. The former has a hydrogen-bonded chain-like structure, while the latter possesses a discrete binuclear structure. 2 on heating in methanol afforded a two-dimensional coordination polymer, [Ag 2 (μ-S-4-py) 2 (PPh 3 ) 2 ] n ( 3 ). The reaction of [Ag 2 (μ-Cl) 2 (PPh 3 ) 4 ] with NaSe-4-py gave [Ag 3 (μ-Se-4-py) 3 (PPh 3 ) 4 ] ( 4 ) as the primary product together with a minor mononuclear complex, [Ag(Se-4-py)(PPh 3 ) 3 ] ( 5 ). The latter could be obtained in excellent yield under the same conditions utilising [AgCl(PPh 3 ) 3 ] as the starting material. Complex 5 on recrystallization afforded 4 . The reaction of [AgCl(PPh 3 ) 3 ] with NaS-2-py yielded [Ag(S-2-py)(PPh 3 ) 3 ] ( 6 ). Complexes 2–6 on refluxing in chloroform gave insoluble polymeric complexes of composition [Ag(Epy)] n ( 7 ) (Epy = 4-pyS ( 7a ), 4-pySe ( 7b ), 2-pyS ( 7c )) which on thermolysis yielded Ag 2 E (E = S, Se). The molecular structures of these complexes ( 1–6 ) have been established unambiguously by single-crystal X-ray diffraction analyses. Non-bonding interactions in the molecular structures have been discussed.