Next Article in Journal
Visible-Light-Mediated Catalyst-Free [2+2] Cycloaddition Reaction for Dihydrocyclobuta[b]naphthalene-3,8-diones Synthesis under Mild Conditions
Previous Article in Journal
New Meroterpenoid Derivatives from the Pomegranate-Derived Endophytic Fungus Talaromyces purpureogenus
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 28
Issue 22
10.3390/molecules28227652
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation

by
Oksana V. Nesterova
1,*,
Svitlana R. Petrusenko
2,3,
Brian W. Skelton
4 and
Dmytro S. Nesterov
1
1
Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
2
Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Str., 01601 Kyiv, Ukraine
3
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
4
School of Molecular Sciences, M310, University of Western Australia, 35 Stirling Hwy, Perth, WA 6009, Australia
*
Author to whom correspondence should be addressed.
Molecules 2023, 28(22), 7652; https://doi.org/10.3390/molecules28227652
Submission received: 31 October 2023 / Revised: 15 November 2023 / Accepted: 16 November 2023 / Published: 18 November 2023
Browse Figures
Versions Notes

Abstract

Three novel heterometallic Ni/Cd coordination compounds [Ni(en)3][CdCl4]∙3dmso (1), [Ni(en)2(dmf)2][CdBr4] (2), and [Ni(en)3]2[CdI4](I)2 (3) have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NH4X (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for 1) or dmf (for 2 and 3). Formation of the one- (1) or three-dimensional (2 and 3) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX4]2− counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)3]2+ and [Ni(en)2(dmf)2]2+ cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations. The non-covalent intermolecular contacts between the cationic nickel and anionic cadmium blocks in the solid state were investigated by the QTAIM analysis. The mechanism of ligand substitution at the nickel center in [Ni(en)2(dmf)2]2+ was theoretically investigated at the ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP level. The results demonstrate that thermodynamic factors are structure-determining ones due to low energy barriers of the rotation of dmf ligands in [Ni(en)2(dmf)2]2+ (below 3 kcal mol−1) and the reversible transformation of [Ni(en)2(dmf)2]2+ into [Ni(en)3]2+ (below 20 kcal mol−1).
Keywords: nickel; cadmium; heterometallic complexes; ethylenediamine; DFT calculations; reaction mechanisms nickel; cadmium; heterometallic complexes; ethylenediamine; DFT calculations; reaction mechanisms
Graphical Abstract

Share and Cite

MDPI and ACS Style

Nesterova, O.V.; Petrusenko, S.R.; Skelton, B.W.; Nesterov, D.S. Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation. Molecules 2023, 28, 7652. https://doi.org/10.3390/molecules28227652

AMA Style

Nesterova OV, Petrusenko SR, Skelton BW, Nesterov DS. Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation. Molecules. 2023; 28(22):7652. https://doi.org/10.3390/molecules28227652

Chicago/Turabian Style

Nesterova, Oksana V., Svitlana R. Petrusenko, Brian W. Skelton, and Dmytro S. Nesterov. 2023. "Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation" Molecules 28, no. 22: 7652. https://doi.org/10.3390/molecules28227652

APA Style

Nesterova, O. V., Petrusenko, S. R., Skelton, B. W., & Nesterov, D. S. (2023). Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation. Molecules, 28(22), 7652. https://doi.org/10.3390/molecules28227652

Article Metrics

Back to TopTop