Quantum chemical study of the addition effect on the geometry of the [Mo6S8(CN)6]6− cluster

Interaction of mononuclear Ni complexes with [M6S8(CN)6]q– clusters (M = Re, Mo): a quantum chemical study

“…In all cases, the geometry optimization of the [Re 6 S 8 (CN) 6 (Ni(H 2 O) 4 ) n ] q systems leads to structures with a very small Re octahedron distortion. At the same time the calculations on the [Mo 6 S 8 (CN) 6 ] qadducts with the Cr(CO) 4 L fragments showed that inclusion of such groups results in noticeable changes in the basic framework of the Mo 6 octahedron [5]. In this study such distortions were found also in the [Mo 6 S 8 (CN) 6 -Ni(H 2 O) 5 ] 4ion pair.…”

“…In this study such distortions were found also in the [Mo 6 S 8 (CN) 6 -Ni(H 2 O) 5 ] 4ion pair. In [5], the large geometry changes in Mo clusters were partly attributed to the composition of the Cr(CO) 4 L fragments, which include such electronically active groups as CO and PR 3 ligands. However, the calculations with the 'normal' complex Ni(H 2 O) 4 2+ as a ligand showed that in this case the distortions of the Mo 6 core are as large as those in the chromium adducts (Table 1).…”

“…Octahedral chalcocyanide clusters [M 6 X 8 (CN) 6 ] n-(M = Mo, Re, X = S, Se, Te) [1][2][3][4] are promising as a source of heterometallic polymers based on the ambivalent nature of cyanide ion, which allows formation of chains or 2D and 3D networks with intercluster links through transition metal M′ (M′ = Ni, Co, Mn, Fe, Cu) ions {-CN-M′(H 2 O) n -NC-} or through hydrogen bonds. Recently we investigated the influence of coordination of chromium carbonyl complexes to octahe-dral [Mo 6 Q 8 (CN) 6 ] nclusters on the structure of the Mo 6 core [5]. It was shown that this interaction leads to considerable deformation of the metal octahedron.…”