The synthesis and characterization of thiocyanate-isocyanide complexes of palladium(ii)
| Autor: | John L. Burmeister, Robert R. Cooke |
|---|---|
| Rok vydání: | 1973 |
| Předmět: |
Substitution reaction
Steric effects Chloroform Thiocyanate Stereochemistry Isocyanide Organic Chemistry Solid-state chemistry.chemical_element Biochemistry Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound chemistry Silver thiocyanate Materials Chemistry Physical and Theoretical Chemistry Palladium |
| Zdroj: | Journal of Organometallic Chemistry. 63:471-480 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(73)80061-0 |
| Popis: | Summary The syntheses of the complexes [Pd (CNR) 2 (SCN) 2 ] (R=phenyl, cyclohexyl), [Pd(CNR) {P(C 6 H 5 ) 3 } (SCN) 2 ] (R=phenyl, cyclohexyl, p-nitrophenyl), and [Pd(CNC 6 H 5 ) {As(C 6 H 5 ) 3 } (SCN) 2 ], via substitution reactions between the corre sponding cis-dichloro and trans-diiodo derivatives and silver thiocyanate in chloroform solution, are described. Molecular weight, conductivity, near and far infrared (solid state and solution) and solution visible-ultraviolet data are presented for each of the complexes. The thiocyanate complexes were generally isolated as the cis -isomer in the solid state but isomerized completely to the trans -isomer in chloroform solution. The [Pd(CNR) 2 (SCN) 2 ] complexes contain only S-bonded thiocyanates, whereas the [Pd(CNR) {P(C 6 H 5 ) 3 } (SCN) 2 ] complexes contain an appreciable number of N -bonded groups (most probably sterically induced), especially in the solid state. The decomposition of the complexes involves the formation of bridging thiocyanate groups. It is concluded that the isocyanides function primarily as σ-donors in these complexes, their trans-influence being insufficient to promote antisymbiotic behavior on the part of the thiocyanates. |
| Databáze: | OpenAIRE |
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