1233235-58-9Relevant academic research and scientific papers
Carbon-fluorine bond activation in thermolysis reactions of the osmium(IV) perfluorothiolate compounds [Os(SC6F5) 4(P(C6H4X-4)3)] (X = CF3, Cl, F, H, CH3, and OCH3)
Mendoza, Consuelo,Bernes, Sylvain,Torrens, Hugo,Arroyo, Maribel
, p. 2646 - 2659 (2010)
Thermolysis reactions of [Os(SC6F5) 4(P(C6H4X-4)3)] (X = CF3 1, Cl 2, F 3, H 4, CH3 5, and OCH3 6) in refluxing toluene yield compounds [OsF(SC6F5)2(SC 6F4(SC6F5)-2)(P(C6H 4X-4)3)] (1a-6a) and [Os(SC6F5) 2(SC6F4(SC6F5)-2)(C 6H4X-4)] (1b-6b). In addition, [Os(SC6F 5)3(SC6F4(SC6F 5)-2)] (c) is yielded from 1-4 and 6, compounds [OsF(SC 6F5)3(P(C6H4X-4) 3)] [X = CF3 (1e), X = Cl (2e)] are also identified as products of the thermolysis reactions of 1 and 2, while [Os(SC6F 5)2(S2C6F4)(P(C 6H4CH3-4)3)] (5d) is obtained from 5. Compounds c, e, and d are produced in low yields (ca. 2-4%). Formation of all products involves the rupture of ortho C-F bonds. The first complexes systematically detected in these thermolysis reactions are compounds a, which are isomers of the starting complexes. Thus, the C-F activation involves the metal-mediated generation of the covalent Os-F bond. Single-crystal X-ray diffraction studies of the new compounds 4a, 5a, 2b-6b, 2e, and 5d indicate that these compounds consist of five-coordinated metal ions in essentially trigonal-bipyramidal geometries. In addition, thermolysis of the isolated compound [OsF(SC6F5)2(SC6F 4(SC6F5)-2)(P(C6H4CH 3-4)3)] (5a) in refluxing toluene gives rise to [Os(SC6F5)2(SC6F4(SC 6F5)-2)(C6H4CH3-4)] (5b) and [Os(SC6F5)2(S2C 6F4)(P(C6H4CH3-4) 3)] (5d), confirming that compounds a can generate compounds b when the thermolysis is prolonged. Compounds 1a-6a, 2b-6b, 1e, and 2e are investigated in solution by NMR studies, including variable-temperature 19F NMR experiments. These molecules are fluxional. Some of the activation parameters for the dynamic processes are determined.
