Jump to main content
Jump to site search


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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 01 Mar 2018, accepted on 09 Apr 2018 and first published on 10 Apr 2018


Article type: Paper
DOI: 10.1039/C8DT00802G
Citation: Dalton Trans., 2018, Advance Article
  •   Request permissions

    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, Advance Article , DOI: 10.1039/C8DT00802G

Search articles by author

Spotlight

Advertisements