Synthesis and characterization of functionalized N,N '-diphenylformamidinate silver(I) dimers: Solid-state structures and solution properties
UNSPECIFIED. (1999) Synthesis and characterization of functionalized N,N '-diphenylformamidinate silver(I) dimers: Solid-state structures and solution properties. INORGANIC CHEMISTRY, 38 (24). pp. 5571-5578. ISSN 0020-1669Full text not available from this repository.
Functionalized N,N'-diphenylformamidines and their deprotonated silver(I) complexes have been synthesized: silver(I) N,N'-di(4-alkyl)phenylformamidinate (alkyl = methyl, ethyl, n-butyl, and n-hexadecyl) 1-4; silver(I) N,N'-di(4-trifluoromethyl)phenylformamidinate 5, silver(I) N,N'-di(3-methoxy)phenylformamidinate 6, silver(I) N,N'-di(3-methylmercapto)phenylformamidinate 7, silver(I) N, N'-di (2-methoxy)phenylformamidinate 8, silver(I) N,N'-di(2-methylmercapto)phenylformamidinate 9. The effects of increasing the coordination number of the silver(I) centers by donor substituents on the phenyl groups have been investigated by solution and solid-state studies. Variable-temperature proton NMR (223-303 K) for 1-4 shows coupling between the proton attached to the amidinate carbon and the Ag-107/109 centers at room temperature which is unaffected by cooling (2). For the four-coordinate complexes, 8 and 9, such coupling is only observed on cooling. Molecular weight measurements recorded in solution by vapor pressure osmometry at 310 K show some aggregation to higher molecular weight species than simple dimers for 1-4 and 6, but 8 and 9 exist as discrete dimeric species. Measurement of thermal stability shows the expected increase in stability with increasing coordination number. Compounds 8 and 9 were structurally characterized by X-ray methods. Both show four-coordinate silver dimers bridged by two amidinate ligands with additional longer interactions with the ether oxygens or thioether sulfurs.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||INORGANIC CHEMISTRY|
|Publisher:||AMER CHEMICAL SOC|
|Official Date:||29 November 1999|
|Number of Pages:||8|
|Page Range:||pp. 5571-5578|
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