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Issue 26, 2017
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Group 2 metal (Mg, Ca, Sr) silylamides supported by a cyclen-derived macrocyclic polyamine

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Abstract

Heteroleptic bis(silyl)amides of magnesium and calcium [(L)M{N(SiMe3)2}] [M = Mg, Ca; LH = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; (Me3TACD)H] were previously synthesized from LH and [M{N(SiMe3)2}2]. Strontium bis(silyl)amides [Sr{N(SiMe3)2}2(thf)2] and [Sr{N(SiHMe2)2}2(thf)2/3] reacted with LH to give different types of products, depending on the presence of the β-SiH function. While the former underwent protonolysis to give the amido-bridged dimer [(L)Sr{N(SiMe3)2}]2 (1), the latter gave the adduct [(LH)Sr{N(SiHMe2)2}2] (2) as a stable solid. 2 slowly underwent an intramolecular Si–H/H–N dehydrocoupling in solution to give [{(L)SiMe2N(SiHMe2)}Sr{N(SiHMe2)2}] (3) by liberating H2. The results of transamination of 1 with HN(SiHMe2)2 depended on the relative stoichiometric ratio. A 1 : 1 mixture in n-pentane gave [{(L)SiMe2N(SiHMe2)}Sr{N(SiMe3)2}] (4) and H2, while excess HN(SiHMe2)2 gave the adduct 2 under similar conditions. Compounds 2 and 3 exhibit Sr↼H–Si interactions according to X-ray crystallography, NMR, and IR spectroscopy. Lighter congeners of elusive [(L)Sr{N(SiHMe2)2}] were isolable for Mg (5) and Ca (6).

Graphical abstract: Group 2 metal (Mg, Ca, Sr) silylamides supported by a cyclen-derived macrocyclic polyamine

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Publication details

The article was received on 11 May 2017, accepted on 01 Jun 2017 and first published on 02 Jun 2017


Article type: Paper
DOI: 10.1039/C7DT01727H
Citation: Dalton Trans., 2017,46, 8451-8457
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    Group 2 metal (Mg, Ca, Sr) silylamides supported by a cyclen-derived macrocyclic polyamine

    D. Mukherjee, S. Shirase, K. Beckerle, T. P. Spaniol, K. Mashima and J. Okuda, Dalton Trans., 2017, 46, 8451
    DOI: 10.1039/C7DT01727H

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