Issue 36, 2018

Salt metathesis routes to homoleptic near-linear Mg(ii) and Ca(ii) bulky bis(silyl)amide complexes

Abstract

Herein we investigate salt metathesis reactions of bulky bis(silyl)amide potassium salts [K{N(SiMe2tBu)2}]n, [K{N(SiMe2tBu)(SiiPr3)}]n, [K{N(SiiPr3)2}]n and [K{N(SiPh3)2}]n (1) with AeI2 (Ae = Mg, Ca, Sr) in an effort to synthesise rare homoleptic two-coordinate complexes. Recrystallization of 1 from THF provided structural authentication of the solvated adduct [K{N(SiPh3)2}(THF)3] (1-THF). For Ae = Mg we were able to identify products for three of the four bis(silyl)amides investigated: [Mg{N(SiMe2tBu)2}2(THF)] (2), [Mg{N(SiMe2tBu)(SiiPr3)}2] (3) and [Mg{N(SiPh3)2}2] (4). Complexes 2–4 were isolated in good yields, and on one occasion during recrystallization of 2 a crystal of the heteroleptic complex [Mg{N(SiMe2tBu)2}(I)(THF)2] (5) was identified by XRD. We found that these methodologies were not widely applicable for larger Ae = Ca and Sr, as large quantities of the parent bis(silyl)amines formed in reaction mixtures; however, we were able to isolate the first near-linear Ca(II) amide [Ca{N(SiiPr3)2}2] (6) from these studies. No Ae-containing products could be isolated from KC8/crown ether reductions of 3, 4 and 6. Complexes 1–4 and 6 were characterised by single crystal XRD, multinuclear NMR and FTIR spectroscopy and elemental analysis, whereas complex 5 was identified by single crystal XRD only.

Graphical abstract: Salt metathesis routes to homoleptic near-linear Mg(ii) and Ca(ii) bulky bis(silyl)amide complexes

Supplementary files

Article information

Article type
Paper
Submitted
01 mrt 2018
Accepted
09 apr 2018
First published
10 apr 2018

Dalton Trans., 2018,47, 12526-12533

Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

J. Leng, C. A. P. Goodwin, Iñigo. J. Vitorica-Yrezabal and D. P. Mills, Dalton Trans., 2018, 47, 12526 DOI: 10.1039/C8DT00802G

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