Issue 5, 2016

Heptaphosphide cluster anions bearing group 14 element amide functionalities

Abstract

Reactions of the protonated heptaphosphide dianion, [HP7]2−, with one equivalent of E[N(SiMe3)2]2 (E = Ge, Sn, Pb) give rise to novel derivatized cluster anions [P7EN(SiMe3)2]2− (E = Ge (1), Sn (2) and Pb (3)). All three species were characterized by multi-element solution-phase NMR spectroscopy and electrospray ionization mass spectrometry. In addition, 1 and 2 were structurally authenticated by means of single crystal X-ray diffraction in [K(18-crown-6)]2[P7EN(SiMe3)2]·2py. Interestingly, while 2 appears to be indefinitely stable in solution for prolonged periods of time, the germanium-containing analogue, 1, readily decomposes at room temperature giving rise to the dimeric species [(P7Ge)2N(SiMe3)2]3− (4) and [K(18-crown-6)][N(SiMe3)2]. A low quality single crystal X-ray structure of the former allowed for the confirmation of its composition and connectivity which is consistent with the 31P NMR spectrum obtained for the anion.

Graphical abstract: Heptaphosphide cluster anions bearing group 14 element amide functionalities

Supplementary files

Article information

Article type
Paper
Submitted
23 Jun 2015
Accepted
17 Jul 2015
First published
17 Jul 2015

Dalton Trans., 2016,45, 1930-1936

Author version available

Heptaphosphide cluster anions bearing group 14 element amide functionalities

G. E. Quintero, I. Paterson-Taylor, N. H. Rees and J. M. Goicoechea, Dalton Trans., 2016, 45, 1930 DOI: 10.1039/C5DT02380G

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