European Journal of Inorganic Chemistry p. 4481 - 4493 (2018)
Update date:2022-08-16
Topics:
Murphy, Luke J.
Ruddy, Adam J.
McDonald, Robert
Ferguson, Michael J.
Turculet, Laura
The syntheses of CoII halide complexes supported by κ3-(2-Cy2PC6H4)2SiMe (Cy-PSiP) ligation are detailed. Reduction of (Cy-PSiP)Co(PMe3)I could be achieved under mild conditions using magnesium metal to generate the CoI complex (Cy-PSiP)Co(PMe3)N2 in high yield. When this reaction was carried out under an atmosphere of CO, (Cy-PSiP)Co(CO)2 was obtained. Unlike the facile reduction of CoII to CoI, attempts to access CoIII species supported by Cy-PSiP ligation proved challenging. Attempted oxidative addition reactions involving (Cy-PSiP)Co(PMe3)N2 were generally unsuccessful, with the sole exception of H2, which reacted to afford the dihydride complex (Cy-PSiP)Co(PMe3)(H)2. The dihydride complex undergoes Co-H site exchange in solution and readily eliminates H2. The CoI precursor (Cy-PSiP)Co(PMe3)N2 is a competent precatalyst for the hydrogenation of terminal alkenes. Exposure of (Cy-PSiP)CoI to O2 gas under anhydrous conditions led to rapid ligand oxidation at Si and P, with no evidence observed at low temperature for a CoIII superoxo or peroxo intermediate. Exclusive oxidation at Si to afford a CoII-siloxy complex was observed upon treatment of (Cy-PSiP)CoI with one equiv. Me3NO. While this siloxy complex did not react further with O2, treatment with a second equiv. of Me3NO led to subsequent oxidation involving one phosphino donor. This observation supports the notion that in the ligand oxidation reactivity observed with O2, the O atoms incorporated at both Si and P are likely derived from the same O2 molecule.
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