Issue 28, 2008

Magnesium amido N-heterocyclic carbene complexes

Abstract

Magnesium dications bind strongly to a tridentate anionic dicarbene ligand L = [N{CH2CH2(CNCHCHNMes)}2] forming dinuclear and trinuclear Mg complexes with some particularly short Mg–C bonds. Treatment of the proligand H4LCl3 with three equivalents of methyl magnesium chloride or benzyl magnesium chloride affords Mg3(HL)Cl6 in high yield. A suspension of 1 in thf was heated to 80 °C for 2 h to afford Mg2(L)Cl3, consistent with the loss of one equivalent of MgCl2, and the deprotonation of the remaining acidic NH, lost as HCl gas. Treatment of Mg3(HL)Cl6 with one equivalent of KC8 results in deprotonation of the ligand amine NH to afford Mg3(L)Cl5; treatment with a second equivalent forms the radical anion of the complex, K[Mg3(L)Cl5], which decomposes upon storage, precluding its structural characterisation. The acidic NH proton of the ligand in Mg3(HL)Cl6 can also be removed by deprotonation with Li{N(SiMe3)2}; additional equivalents of which also exchange the magnesium-bound chlorides for silylamido ligands, affording Mg2(L)Cl2N″ and Mg2(L)Cl(N″)2, which have both been characterised by single-crystal X-ray diffraction studies.

Graphical abstract: Magnesium amido N-heterocyclic carbene complexes

Supplementary files

Article information

Article type
Paper
Submitted
25 Feb 2008
Accepted
24 Apr 2008
First published
09 Jun 2008

Dalton Trans., 2008, 3739-3746

Magnesium amido N-heterocyclic carbene complexes

P. L. Arnold, I. S. Edworthy, C. D. Carmichael, A. J. Blake and C. Wilson, Dalton Trans., 2008, 3739 DOI: 10.1039/B803253J

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