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Metal‐mediated Ring Opening Reaction of Two Aziridines to give 1,2‐Aminoaziridinoethane Ligands
Author(s) -
Krinninger C.,
Ruiz J. C. G.,
Nöth H.,
Lorenz I.P.
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200600393
Subject(s) - chemistry , ligand (biochemistry) , octahedron , crystallography , aziridine , ring (chemistry) , metal , metal carbonyl , transition metal , coordination sphere , stereochemistry , mass spectrum , medicinal chemistry , crystal structure , catalysis , mass spectrometry , organic chemistry , chromatography , biochemistry , receptor
The reaction of 2,2′‐dimethylaziridine with the carbonyl halogenido complexes [(CO) 5 MX] (M = Mn; X = Cl, I; M = Re: X = I) results in the formation of the 1,2‐aminoaziridinoethane complexes [(CO) 3 XM{NH 2 CMe 2 CH 2 N(C 2 H 2 Me 2 )}]. The bis(2,2′‐dimethylaziridine) complexes [(CO) 3 XM(NHCH 2 CMe 2 ) 2 ] may act as intermediates. The new asymmetric chelate ligand is the formal dimerization product of 2,2′‐dimethylaziridine, which is formed and stabilized in the coordination sphere of both transition metals. The new complexes have been characterized using elemental analysis, mass, IR and NMR spectra as well as by X‐ray structure analysis. The metal centers exhibit a distorted octahedral configuration with a facial (CO) 3 M‐arrangement, and the 5‐membered metallacycles show a twist conformation and lie in the trans ‐positions with respect to the CO ligands in the equatorial plane. Whereas the Mn‐N bonds to the intact aziridine system are longer (213.3 and 213.8 pm) than those to the NH 2 group (206.5 and 207.4 pm), the corresponding Re–N bonds show the opposite trend, whereby the Re–NH 2 bonds are shorter (219.0 and 225.8 pm).