Issue 5, 2019

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-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

Supplementary files

Article information

Article type
Edge Article
Submitted
24 Oct 2018
Accepted
29 Nov 2018
First published
04 Dec 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 1302-1308

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, 10, 1302 DOI: 10.1039/C8SC04745F

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