Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3)

Robertson, Stuart D. and Chivers, Tristram and Konu, Jari (2007) Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3). Journal of Organometallic Chemistry, 692 (20). pp. 4327-4336. ISSN 0022-328X (https://doi.org/10.1016/j.jorganchem.2007.06.064)

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Abstract

Reactions of ((BuHN)-Bu-t)(3)PNSiMe3 (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}] (2), [Me2Al((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)2}] (3) and [Mg{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}(2)] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 center dot 2THF) or one molecule of TMEDA (5 center dot TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me2Al[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)]MgBu} Li center dot 4THF (6 center dot 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al-Me group to give {MeIAI[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)Mg]} (7). Complexes 5 center dot 2THF, 5 center dot TMEDA, 6 center dot 4THF and 7 have been characterized in solution by multinuclear (H-1, C-13, P-31 and Li-7) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 center dot 2THF have been determined by X-ray crystallography. (c) 2007 Elsevier B.V. All rights reserved.

ORCID iDs

Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770, Chivers, Tristram and Konu, Jari;
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