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Mimicking of the histidine brace structural motif in molecular copper(I) compounds
Author(s) -
Peifer R.,
Müller L.,
Hoof S.,
Beckmann F.,
Cula B.,
Limberg C.
Publication year - 2021
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.202100145
Subject(s) - chemistry , copper , histidine , stereochemistry , ligand (biochemistry) , crystal structure , dimer , medicinal chemistry , crystallography , organic chemistry , enzyme , biochemistry , receptor
Abstract L‐Nτ‐methylhistidine methyl ester, MeHisOMe, has been employed as a potential ligand to mimic the histidine brace‐type coordination of copper ions in enzymes such as the particulate methane monoxygenase or lytic polysaccharide monooxygenases. MeHisOMe was prepared by double‐methylation of histidine methyl ester. Subsequently, its complexation by diphosphine copper(I) precursors [Cu(P^P)(MeCN) 2 ]BF 4 was tested, which led to the complexes [Cu(P^P)(MeHisOMe)]BF 4 (P^P=dpePhos: 1 , P^P=XantPhos: 2 , P^P=dppf: 3 ). 1 – 3 were fully characterized, also by single crystal X‐ray analysis, thus providing first structural data for copper complexes with a synthetic, authentic histidine brace. The complexes proved inert in contact with dioxygen. To improve the biomimetic character attempts were made to formally replace the diphosphine ligands by bis(pyrazolyl)methanes, Bpm. Correspondingly, [BpmCu(NCMe) x ]BF 4 precursors were synthesized, with different substituents at the 3‐positions of the pyrazolyl (i. e. Bpm=di(3‐(phenyl)‐1H‐pyrazol‐1‐yl)diphenylmethane, di(3‐(mesityl)‐1H‐pyrazol‐1‐yl)methane and di(3‐( tert ‐butyl)‐1H‐pyrazol‐1‐yl)diphenylmethane). Addition of MeHisOMe to these complexes led to products that were so sensitive towards oxidation by the environment that they eluded isolation. One experiment provided blue crystals as a product of such a reaction. They belonged to a salt with a complex cation consisting of a Cu(μ‐OH) 2 Cu core ligated by two MeHisOMe ligands, which dimerises in the solid state to give [Cu 4 (OH) 4 (MeHisOMe) 4 ] 4+ .