Niobium and tantalum octahedral Halides: Vibrational properties and Intra–Cluster interactions. (1st November 2022)

• Record Type: Journal Article
• Authors: Shamshurin, Maxim V.; Martynova, Svetlana A.; Sokolov, Maxim N.; Benassi, Enrico
• Is Part Of: Polyhedron. Volume 226(2022)
• Publication Date: 2022-11-01
• Subjects: Niobium and tantalum halides -- Vibrational spectroscopies -- Quantum chemical calculations -- Natural bond orbital analysis -- Bader's atoms-in-molecules theory; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2022.116107
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A new light is shed on the electronic structure and intra-cluster interactions of the niobium and tantalum homohalide clusters. The vibrational spectra are quantitatively interpreted on the basis of the composition of the normal modes as a function of the internal coordinates. Four Raman spectra are experimentally recorded and interpreted for the first time. Abstract: IR and Raman spectroscopies are important characterisation methods for Nb and Ta octahedral halide clusters [M6 X i 12 X a 6 ] x (M = Nb, Ta; X = Cl, Br; x = 4–, 3–, 2–; i – "inner", bridging ligand belonging to the cluster core, a – "ausser" or "apical" terminal ligand) and the polymeric Ta6 I14 . The structural and spectroscopic data of these compounds ( x = 4–) and their corresponding {M6 X12 } 2+ core clusters were systematically investigated and analysed by means of quantum chemical calculations. The intra–cluster interactions were studied in details by means of Natural Bond Orbital and Bader's Atoms–In–Molecules theory analyses, and the results were related to the spectroscopical features, in particular to the composition of the main vibrational normal modes in terms of the contribution of the internal coordinates.