Issue 15, 2003

Low coordinate magnesium chemistry supported by a bulky β-diketiminate ligand

Abstract

A series of magnesium(II) alkyl, alkoxide, carboxylate, amide and halide complexes stabilised by the bulky β-diketiminate ligand, HC(C(Me)N-2,6-iPr2C6H3)2 (BDI), have been synthesised and structurally characterised. (BDI)H reacts with MgMe2 in Et2O to give the four-coordinate complex (BDI)MgCH3(Et2O), 1, and in toluene to afford [(BDI)Mg(μ-CH3)]2, 2. Three coordinate complexes may be accessed by increasing the size of the alkyl ligand; hence, the reaction of (BDI)H with tBu2Mg yields (BDI)MgtBu, 3, while Li(BDI) reacts with iPrMgCl to afford (BDI)MgiPr, 4; a similar reaction with PhMgCl affords the diethyl ether adduct (BDI)MgPh(Et2O), 5. The etherates 1 and 5 may be converted into the base-free complexes, 2 and (BDI)MgPh, 6, respectively, upon heating in vacuo. The direct reaction of (BDI)H with RMgX (X = Cl or Br) results in relatively inert halide-bridged dimers of formula [(BDI)Mg(μ-X)]2, (X = Cl, 7; X = Br, 8). The alkylmagnesium derivatives react readily with alcohols, amines or carboxylic acids to yield alkoxide, amide and carboxylate complexes, respectively. For example, 4 reacts with iPrOH (or O2) to form [(BDI)Mg(μ-OiPr)]2, 9. Convenient one-pot synthetic procedures have been developed using commercially available Bu2Mg. Treatment of Bu2Mg with (BDI)H, followed by its reaction with MeOH, tBuOH, iPr2NH, (Me3Si)2NH, MeCO2H or PhCO2H affords [(BDI)Mg(μ-OMe)]2, 10, [(BDI)Mg(μ-OtBu)]2, 11, (BDI)Mg(NiPr2), 12, (BDI)Mg(NTMS2), 13, [(BDI)Mg(μ-O2CMe])]2, 14, and [(BDI)Mg(μ-O2CPh)]2, 15, respectively. The molecular structures of complexes 4–8 and 12–15 are reported.

Graphical abstract: Low coordinate magnesium chemistry supported by a bulky β-diketiminate ligand

Supplementary files

Article information

Article type
Paper
Submitted
31 Mar 2003
Accepted
21 May 2003
First published
01 Jul 2003

Dalton Trans., 2003, 3088-3097

Low coordinate magnesium chemistry supported by a bulky β-diketiminate ligand

A. P. Dove, V. C. Gibson, P. Hormnirun, E. L. Marshall, J. A. Segal, A. J. P. White and D. J. Williams, Dalton Trans., 2003, 3088 DOI: 10.1039/B303550F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements