Bonding Analysis of Inorganic Transition-Metal Cubic Clusters. 6. Copper(I)−Dithiolato Species and Related Compounds

Abstract

Extended Hückel and density functional calculations carried out on 128-MVE Cu(8)(dithiolato)(6) edge-bridged cubic clusters indicate that their stability is mainly driven by the chelating effect of the ligands, which provide a stable 16-electron configuration to the approximately trigonal planar metal centers. Nevertheless, a weak but significant d(10)-d(10) bonding interaction is present which is rather independent from the dithiolato bite effect. The metal centers have a nonbonding 4p(z)() vacant AO pointing to the center of the cube available for bonding to an encapsulated atom. The electronic closed-shell requirement is satisfied for the 136-MVE and 140-MVE counts, respectively, when a main-group atom or a transition-metal atom is incorporated in the middle of the cube. The bonding within these dithiolato compounds is compared to other edge-bridged M(8) cubic clusters. In particular, it is shown that clusters of higher nuclearity but containing an M(8) cubic core are related to the dithiolato species. Indeed, their outer metal atoms can be considered as belonging to the ligand shell, interacting with the M(8) cube in a way similar to the dithiolato ligands in the Cu(8) species.

Plasticity in [(R4–xR1x)4N]4[Cu4{S2C2(CN)2}4] (x = 0–4) is Molded by a Guest Cation on an Elastic Anionic Host

“…The four Cu I ions and mnt ligands form a discrete tetranuclear complex in which each mnt ligand forms a µ 1 -S bond to a Cu atom and a µ 2 -S bond to the same Cu atom to form a fivemembered chelate ring. [21] This mnt ligand further binds to an adjacent Cu atom to build a Cu 4 S 4 eight-membered ring. The average S···S bite distance in mnt is 3.353 Å and the average S-Cu-S angle is 96.8°.…”

Skeletal isomerism in mixed transition-metal/main-group closo clusters

“…A comparison of the available experimental bond distances with the corresponding optimized ones (Table 4) reveals a somewhat overestimation (by 2-6%) of the optimized bond lengths involving heavy atoms. This is a common feature of this type of nonlocal DFT calculations on complexes of transition-metal in low oxidation states [46,54]. We look first at the compounds in which E is a bare atom of group 15.…”

Cluster Growth Reactions with Selenido‐Carbonyl Clusters − Synthesis, Characterisation and Theoretical Study of the Dimetallic closo Clusters [WRu3(μ4‐Se)2(μ‐CO)4(CO)6(L)2] (L = Phosphane) and of the Donor‐Acceptor Adduct [(CO)5W(μ4‐Se)Ru3(μ3‐Se)(CO)7{P(CH2Ph)Ph2}2]

“…The major optimised bond lengths and angles are given in Table 2. Taking into account that such calculations are known to overestimate the bond lengths between heavy atoms by approximately 2Ϫ6%, [15] the optimised geometry of [WRu 3 (µ 4 -Se) 2 (µ-CO) 4 (20) as the only isolable product identified by X-ray diffraction methods. It could be considered as the product of a donoracceptor interaction between a W(CO) 5 fragment and a selenido ligand of 10.…”