Influence of the ligand on the coupling between the metal-based electrons in face-shared [M2X9]3- (M = Mo, W; X = F, Cl, Br, I) systems
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Updated: Sep 20, 2026

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Germán Cavigliasso1, Robert Stranger
1Department of Chemistry, Faculty of Science, Australian National University, Canberra ACT 0200, Australia.
Abstract:
Orbital overlap and spin polarization effects in Mo and W [M(2)X(9)](3)(-) halide and in [M(2)X'(3)X' '(6)](3)(-) mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M(2)X(9)](3)(-) systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M(2)X'(3)X' '(6)](3)(-) systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.
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