Issue 8, 2002

Structural and synthetic studies of magnesium and zinc tolylformamidinate complexes

Abstract

The reaction of MgBu2 with 2.0 equivalents of di(p-tolyl)formamidine (HFTolP) affords the colourless crystalline bis(formamidinate) species [Mg(FTolP)2(thf)2] (1), [Mg(FTolP)2(dme)]·DME (3) and [Mg(FTolP)2(tmeda)] (4) in moderate to high yield when conducted in tetrahydrofuran, 1,2-dimethoxyethane and toluene–TMEDA, respectively. Compounds 1, 3, 4 and the di(o-tolyl)formamidinate (FTolO) complex; [Mg(FTolO)2(thf)2] (2), synthesised in a manner identical to that employed for the preparation of 1, have been characterised by spectroscopy (1H NMR, 13C NMR, FTIR) and single crystal XRD. In the solid state, all four species display monomeric octahedral bis(η2-formamidinate) metal centres that differ solely on the basis of the steric and structural requirements of both the coordinating solvent donor and the formamidinate. Attempts to prepare analogous zinc complexes via the treatment of anhydrous ZnCl2 with 2.0 equivalents of the known complex [{Li(FTolP)(Et2O)}2], or treatment of HFTolP with 0.5 equivalents of ZnEt2 primarily yielded the novel lithium zincate species [(μ5-O)Li2Zn3{(p-tolyl)NC(H)N(O)(p-tolyl)}6] (5), which includes a trapped dilithium oxygen unit, and the precedented tetrazinc oxygen cluster [(μ4-O)Zn4(FTolP)6] (6), respectively. The molecular structures of complexes 16 are discussed, as are alternative routes to species 6.

Graphical abstract: Structural and synthetic studies of magnesium and zinc tolylformamidinate complexes

Supplementary files

Article information

Article type
Paper
Submitted
03 May 2002
Accepted
14 May 2002
First published
25 Jun 2002

New J. Chem., 2002,26, 1015-1024

Structural and synthetic studies of magnesium and zinc tolylformamidinate complexes

M. L. Cole, D. J. Evans, P. C. Junk and L. M. Louis, New J. Chem., 2002, 26, 1015 DOI: 10.1039/B204304A

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