Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt

Abstract

Rare mono- and diorganopentaphosphido cobalt complexes are accessible by P–P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)₂{(^MesBIAN)Co(μ-η⁴:η²-P₄)Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et₂O){(^MesBIAN)Co(η⁴-1,5-cod)}] [1, BIAN = bis(mesitylimino)acenaphthene diimine, cod = 1,5-cyclooctadiene] with [Ga(nacnac)(η²-P₄)] (nacnac = CH[CMeN(2,6-iPr₂C₆H₃)]₂). Reactions with R₂PCl (R = iPr, tBu, and Cy) selectively afford [(^MesBIAN)Co(cyclo-P₅R₂)] (3a–c), which feature η⁴-coordinated 1,1-diorganopentaphosphido ligands. The mechanism of formation of these species has been studied by ³¹P{¹H} NMR spectroscopy and DFT calculations. In the case of 3a (R = iPr), it was possible to identify the intermediate [(^MesBIAN)Co(μ-η⁴:η²-P₅iPr₂)Ga(nacnac)] (4) by single-crystal X-ray diffraction. A related, monosubstituted organopentaphosphido cobalt complex [(^MesBIAN)Co(μ-η⁴:η¹-P₅tBu)GaCl(nacnac)] (5) was isolated by reacting dichloroalkylphosphane tBuPCl₂ 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.