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

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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-η42-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-η42-P5iPr2)Ga(nacnac)] (4) by single-crystal X-ray diffraction. A related, monosubstituted organopentaphosphido cobalt complex [(MesBIAN)Co(μ-η41-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.

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

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Publication details

The article was received on 24 Oct 2018, accepted on 29 Nov 2018 and first published on 04 Dec 2018


Article type: Edge Article
DOI: 10.1039/C8SC04745F
Citation: Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
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    Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt

    C. G. P. Ziegler, T. M. Maier, S. Pelties, C. Taube, F. Hennersdorf, A. W. Ehlers, J. J. Weigand and R. Wolf, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C8SC04745F

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