Universität zu Köln

Stevenson, Brandon C., Peckelsen, Katrin, Martens, Jonathan, Berden, Giel, Oomens, Jos ORCID: 0000-0002-2717-1278, Schaefer, Mathias and Armentrout, P. B. (2021). An investigation of inter-ligand coordination and flexibility: IRMPD spectroscopic and theoretical evaluation of calcium and nickel histidine dimers. J. Mol. Spectrosc., 381. SAN DIEGO: ACADEMIC PRESS INC ELSEVIER SCIENCE. ISSN 1096-083X

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Abstract

Metallated gas-phase structures consisting of an intact and deprotonated histidine (His) ligand, M(His-H)(His)+, where M = Ca and Ni, were examined using infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light from a free-electron laser (FEL). In parallel, ab initio quantum-chemical calculations identified several low-energy isomers for each complex. Experimental action spectra were compared to linear absorption spectra calculated at the B3LYP level of theory, using the 6-311+G(d,p) basis set. Single-point energies were calculated at B3LYP, B3LYP-GD3BJ, B3P86, and MP2(full) levels using the 6-311+G(2d,2p) basis set. For Ca(His-H)(His)+, the dominant structure has the metal center coordinating with the pi nitrogen of the imidazole ring (N pi) and both oxygen atoms of the carboxylate group of the deprotonated His ligand while coordinating with the backbone amine (N alpha), N pi, and the carbonyl oxygen of the carboxylic acid of the intact His ligand. The Ni(His-H)(His)+ species coordinates the metal ion through N alpha, N pi, and the carbonyl oxygen for both the deprotonated and intact His ligands, but also shows evidence for a minor secondary structure where the deprotonated His coordinates the metal at N alpha, N pi, and the deprotonated carbonyl oxygen and the intact His ligand is zwitterionic, coordinating the metal with both carboxylate oxygens. Different levels of theory predict different ground structures, highlighting the need for utilizing multiple levels of theory to help identify the gasphase structure actually observed experimentally.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Stevenson, Brandon C. UNSPECIFIED UNSPECIFIED UNSPECIFIED Peckelsen, Katrin UNSPECIFIED UNSPECIFIED UNSPECIFIED Martens, Jonathan UNSPECIFIED UNSPECIFIED UNSPECIFIED Berden, Giel UNSPECIFIED UNSPECIFIED UNSPECIFIED Oomens, Jos UNSPECIFIED orcid.org/0000-0002-2717-1278 UNSPECIFIED Schaefer, Mathias UNSPECIFIED UNSPECIFIED UNSPECIFIED Armentrout, P. B. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-588115
DOI:	10.1016/j.jms.2021.111532
Journal or Publication Title:	J. Mol. Spectrosc.
Volume:	381
Date:	2021
Publisher:	ACADEMIC PRESS INC ELSEVIER SCIENCE
Place of Publication:	SAN DIEGO
ISSN:	1096-083X
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language METAL CATION SIZE; PHOTON DISSOCIATION SPECTROSCOPY; COMPLEXES; ZN2+; STABILITY; SPECTRA; SERINE; CHARGE; CD2+ Multiple languages Physics, Atomic, Molecular & Chemical; Spectroscopy Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/58811