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• W2365121024 abstract "During the past few years a series of systematic crystal structure analyses and chemical reactivity studies have been carried out in our Institute and Research Laboratory on the following [Mo3S4]4+ cluster. [Mo3(μ3-Sc)(μ-Sb)3(x-dtp)3(μ-dtp)(OH2)](Ⅰ),where dtp ={S2P(OEt)2}- (Fig. 1). It is shown in ref. (1)that the non-planar puckered [Mo3S3] cluster ring in I exhibits quasi-aromaticity, as pointed out by J-Q Huang on the basis of structural and chemical evidences. Structurally, the 6 Mo -Sb bonds have an average length of (2. 281±0. 017) A , intermediate between the single-bond Mo - S length 2. 44A and the double-bond Mo=S length of 2. 08A , whereas the 6 bond angles fall into two sets of (96. 6±0. 7)° for ∠(S-Mo-S) and (7. 43±0. 8°) for ∠(Mo - S - Mo). With regard to its chemical reactivity (cf. Figs. 2-4), the following regularities are worthy of note. Thus the reactivity sequence for ligand substitution reactions is OH2μ-dtpx-dtpSc, with the [Mo3S3] ring kept intact and practically invariant in the course of these reactions. There are two types of addition reactions: simultaneous addition of 3 S atoms with the formation of 3 μ-S2 ; addition of 1 M atom alone to form, for instance [(Mo3S4)Cu]5+ or [{Mo3S4}2Mo]8+, with the entire [Mo3S4]4+ entering into these reactions as a whole. On the other hand, oxidation of one of the 3 Sb atoms is at once accompanied by the rupture of 2 adjoining Mo-Sb bonds and the formation of 2 new Mo=O bonds. The resemblances to C6H6 in all these respects are very striking. Elucidation of the nature of such a quasi-aromaticity is undoubtelly an interesting theoretical problem. A reasonable quantum-chemical picture of this Mo-S cluster 1 can be obtained by the use of energy-localized LMO's calculated under the CN-DO/2 approximation by the Edmiston-Ruedenberg technique, at different structural complexity levels; the [Mo3S3] cluster ring, the [Mo3S4] cluster core, and the whole cluster molecule. We are therefore able to compare the delocalized electronic structure of I with pictures similarly obtained for the aromatic [C6 ] core in C6H6 and the quasi-aromatic [B3X3] (X=N,O) cores in B3N3H6 and (B3O6)3- , and arrive at a much deeper insight into the nature of quasi-aromaticity.In C6H6 (cf. Table 1; Fig. 5) the LMO's for the 12 lower-energy levels obviously correspond tothe 6 σ(C-C) and 6 σ(C - H) bonds of the valence bond theory. Those for the next 3 higher levels,on the other hand, turn out to correspond to 3 three-center two-electron bondsin the 3islands more or less in the sense of Dewar[6], although these are not at all isolated from each other. Each pair of these adjoining islands shares the only pz AO of the common C atom, with a rather large calculated interaction energy of - 0. 1 i 6 a. u. Thus these 3 three-center π bonds interact with each other to form a large closed conjugated it orbital system with a rather large additional stabilization energy. The correctness of this picture is entirely confirmed by a similar calculation carried out for the linear hexatriene C6H8, which shows clearly only 3 alternately localized ordinary two-center n bonds. We are therefore led to the conclusion that this triad of 3 adjoining three-center π bonds, cooperating with each other to form a closed conjugated π orbital system, is the most significant microscopic feature of these aromatic compounds. In the two [B3X3] clusters (cf. Fig. 5 Table 1), there are again, besides the 6 σ(B -X)and the 3 σ (B - Yt) (Yt = H, Ot) bonds etc. , 3three center two-electron(p~p-p)π bonds in the 3islands with somewhatsmaller calculated interaction energies of -0. 095 and - 0. 077 a. u. , for X=N,O respectively, yet large enough to form a sufficiently large closed conjugated π orbital system. There is, however, one notable difference between C6H6 and [B3X3]. In the latter case, in each of the islands the 2 elec-trons are contributed solely by the lone pair occupying the p2 AO of the more electronegative atom X, while each of the 2 B atoms provides an empty p2 AO,thus forming the three-center" @default.
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• W2365121024 date "1989-01-01" @default.
• W2365121024 modified "2023-09-23" @default.
• W2365121024 title "A Preliminary Discussion of the Nature of Quasi-Aromaticity in the Non-Planar Puckered [Mo_3S_3] Rings of Certain [Mo_3S_4]~(4+) Clusters" @default.
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