Universität zu Köln

Safin, Damir A., Babashkina, Maria G., Bolte, Michael, Mitoraj, Mariusz P. and Klein, Axel ORCID: 0000-0003-0093-9619 (2015). Metal ion influences distortion of the ligand in the structure of [M{2-MeO(O)CC6H4NHC(S) NP(S)-(OiPr)(2)}(2)] (M = Zn-II, Cd-II) complexes: a driving force for intermolecular aggregation. Dalton Trans., 44 (31). S. 14101 - 14110. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

Reaction of the in situ deprotonated N-thiophosphorylated thiourea 2-MeO(O)CC6H4NHC(S) NHP(S)-( OiPr)(2)(HL) with MCl2 (M = Zn-II, Cd-II) in aqueous ethanol leads to complexes of the formula [ML2]. Both compounds crystallise in the triclinic space group P (1) over bar with Z = 2 and the metal cations are found in a tetrahedral S2S'(2) coordination environment formed by the C-S and P-S sulfur atoms. The crystal structures reveal intramolecular N-H center dot center dot center dot O=C hydrogen bonds formed within the 2-MeO(O)CC6H4NH fragments. Both structures are further stabilised by intermolecular pi center dot center dot center dot pi stacking interactions, which are more efficient in [CdL2]. Here, a pronounced dimeric intermolecular aggregate is observed which goes along with a pronounced distortion of the chelate [(S)CNP(S)](-) backbone of the ligand upon coordination to CdII as well as a significantly distorted coordination tetrahedron CdS2S'(2). The aggregation is also reflected in the positive electrospray ionisation (ESI) mass spectrum of the Cd-II complex, which exhibits peaks for the dimeric cations [Cd2L3](+), [Cd2L4 + H](+) and [Cd2L4 + Na](+), while for the Zn-II analogue only monomeric species were observed. Quantum chemical ETS-NOCV (ADF) calculations confirm the higher stability of dimers in [CdL2] compared with [ZnL2]. The pi center dot center dot center dot pi stacking interactions are prodominantly due to dispersion contributions, though the electrostatic and orbital interaction components are also important. QTAIM (ADF) type calculations additionally quantify the covalent and non-covalent interactions in the momomers.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Safin, Damir A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Babashkina, Maria G. UNSPECIFIED UNSPECIFIED UNSPECIFIED Bolte, Michael UNSPECIFIED UNSPECIFIED UNSPECIFIED Mitoraj, Mariusz P. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-416197
DOI:	10.1039/c5dt02189h
Journal or Publication Title:	Dalton Trans.
Volume:	44
Number:	31
Page Range:	S. 14101 - 14110
Date:	2015
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CRYSTAL-STRUCTURES; COORDINATION CHEMISTRY; ZINC(II) COMPLEXES; STACKING INTERACTIONS; CD(II) COMPLEXES; HYDROGEN-BOND; THIN-FILMS; ZN(II); CADMIUM(II); DIVERSITY Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41619