Zusammenfassung
Rare mono-and diorganopentaphosphido cobalt complexes are accessible by P-P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)(2){((Mes)BIAN) Co(mu-eta(4):eta(2)-P-4) Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et2O){(MesBIAN) Co(h 4-1,5cod)}] [1, BIAN = bis(mesitylimino) acenaphthene diimine, cod = 1,5-cyclooctadiene] with ...
Zusammenfassung
Rare mono-and diorganopentaphosphido cobalt complexes are accessible by P-P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)(2){((Mes)BIAN) Co(mu-eta(4):eta(2)-P-4) Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et2O){(MesBIAN) Co(h 4-1,5cod)}] [1, BIAN = bis(mesitylimino) acenaphthene diimine, cod = 1,5-cyclooctadiene] with [Ga(nacnac)(eta(2)-P4)] (nacnac = CH[CMeN(2,6-iPr(2)C(6)H(3))](2)). Reactions with R2PCl (R = iPr, tBu, and Cy) selectively afford [((Mes)BIAN)Co(cyclo-P5R2)] (3a-c), which feature eta(4)-coordinated 1,1-diorganopentaphosphido ligands. The mechanism of formation of these species has been studied by P-31{H-1} NMR spectroscopy and DFT calculations. In the case of 3a (R = iPr), it was possible to identify the intermediate [((Mes)BIAN)Co(mu-eta(4):eta(2)-P(5)iPr(2)) Ga(nacnac)] (4) by single-crystal X-ray diffraction. A related, monosubstituted organopentaphosphido cobalt complex [((Mes)BIAN)Co(mu-eta(4):eta(1)-P(5)tBu) GaCl(nacnac)] (5) was isolated by reacting dichloroalkylphosphane tBuPCl(2) with 2. Heterobimetallic complexes such as 2 thus may enable the targeted construction of a range of new metal-coordinated polyphosphorus frameworks by P-P condensation.
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