Issue 13, 2012

Iron(ii) complexes of new hexadentate 1,1,1-tris-(iminomethyl)ethane podands, and their 7-methyl-1,3,5-triazaadamantane rearrangement products

Abstract

New iron(II) podand complexes have been prepared, by condensation of 2-(aminomethyl)-2-methyl-1,3-diaminopropane with 3 equiv of a heterocyclic aldehyde in the presence of hydrated Fe[BF4]2 or Fe[ClO4]2 as templates. The 2-(aminomethyl)-2-methyl-1,3-diaminopropane is prepared in situ by deprotonation of its trihydrochloride salt. The chloride must be removed from these reactions by precipitation with silver, to avoid the formation of the alternative 2,4,6-trisubstituted-7-methyl-1,3,5-triazaadamantane condensation products, or their FeCl2 adducts. The crystal structures of two 2,4,6-tri(pyridyl)-7-methyl-1,3,5-triazaadamantane-containing species are presented, and contain two different geometric isomers of this tricyclic ring with three equatorial, or two equatorial and one axial, pyridyl substituents. Both structures feature strong C–H⋯X (X = Cl or F) hydrogen bonding from the aminal C–H groups in the triazaadamantane ring. Five iron(II) podand complexes were successfully obtained, all of which contain low-spin iron centres.

Graphical abstract: Iron(ii) complexes of new hexadentate 1,1,1-tris-(iminomethyl)ethane podands, and their 7-methyl-1,3,5-triazaadamantane rearrangement products

Supplementary files

Article information

Article type
Paper
Submitted
11 Oct 2011
Accepted
05 Dec 2011
First published
11 Jan 2012

Dalton Trans., 2012,41, 3731-3739

Iron(II) complexes of new hexadentate 1,1,1-tris-(iminomethyl)ethane podands, and their 7-methyl-1,3,5-triazaadamantane rearrangement products

S. A. Diener, A. Santoro, C. A. Kilner, J. J. Loughrey and M. A. Halcrow, Dalton Trans., 2012, 41, 3731 DOI: 10.1039/C2DT11911K

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