Universität zu Köln

Zhang, Jun and Dolg, Michael ORCID: 0000-0002-0538-0837 (2015). Labile Capping Bonds in Lanthanide(III) Complexes: Shorter and Weaker. J. Phys. Chem. A, 119 (4). S. 774 - 781. WASHINGTON: AMER CHEMICAL SOC. ISSN 1089-5639

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Abstract

For a wide range of trivalent lanthanide ion coordination complexes of tricapped trigonal prism or monocapped square antiprism configurations, the bonds between the central lanthanide ions and the capping ligands are found to violate Badgers rule: they can get weaker as they get shorter. We demonstrate that this observation originates from the screening and repulsion effect of the prism ligands. Both effects enhance as the electric field of the central ion or the softness of the prism ligands increases. Thus, for heavier lanthanides, despite the fact that the capping bond could be shorter, it is more efficient to be weakened by the prism ligands, being inherently labile. This concept of labile capping bonds phenomenon is then successfully used to interpret many problems in lanthanide(III) hydration, e.g., why the water exchange rate of a lanthanide(III) complex is much higher in a twisted square antiprism than in square antiprism configuration. Thus, the theory proposed in this paper offers new insights in understanding chemical problems.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Zhang, Jun UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-414251
DOI:	10.1021/jp511043c
Journal or Publication Title:	J. Phys. Chem. A
Volume:	119
Number:	4
Page Range:	S. 774 - 781
Date:	2015
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1089-5639
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Theoretical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language INTERNUCLEAR DISTANCES; WATER EXCHANGE; PSEUDOPOTENTIALS; HYDROGEN; IONS Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41425