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Hexaaza‐dithia Macrocycles Containing Pendant Methoxyethyl Groups: Synthesis and Characterization of Mono and Dinuclear Nickel Complexes
Author(s) -
Gressenbuch Mathias,
Kersting Berthold
Publication year - 2016
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.201600117
Subject(s) - chemistry , nickel , reagent , nitrogen atom , nitrogen , naphthalene , medicinal chemistry , stereochemistry , crystallography , polymer chemistry , ring (chemistry) , organic chemistry
The deprotection of two bicyclic hexaaza‐dithioether macrocycles 1 and 2 containing four (or six) N ‐bound 2‐methoxyethyl substituents was achieved in good yields utilizing Li or Na/naphthalene in THF as the reagent. The ability of the resulting hexaaza‐dithiophenolate macrocycles (H 2 L4 and H 2 L5) to act as mono‐ and dinucleating ligands is also demonstrated. Three nickel complexes, namely [Ni(H 2 L4)][BPh 4 ] 2 ( 3 ), [Ni 2 (L4)(μ‐OAc)][BPh 4 ] ( 4 ), and [Ni 2 (L5)(μ‐OAc)][BPh 4 ] ( 5 ), were obtained and characterized by elemental analyses, ESI mass spectrometry, IR and UV/Vis spectroscopy, and in case of 3 and 4 also by X‐ray crystallography. The five‐coordinate nickel atom in complex 3 was found to interact only weakly with one of the four 2‐methoxyethyl groups. The nickel atoms in dinuclear 4 and 5 are coordinatively saturated by the nitrogen and sulfur donor atoms of the macrocycle and the oxygen atoms of the bridging acetato coligands, such that the methoxyethyl substituents function only as dangling groups.