Comparison of the electronic properties of bis(disulfido)dioxidi-.mu.-sulfidodimolybdate(2-) and bis(disulfido)disulfidodi-.mu.-sulfidodimolybdate(2-)

Autor:	Jerry Bernholc, E. I. Stiefel
Rok vydání:	1986
Předmět:	chemistry.chemical_classification Chemistry Stereochemistry Electronic structure Triple bond Antibonding molecular orbital Inorganic Chemistry Crystallography Atomic orbital Reactivity (chemistry) Molecular orbital Physical and Theoretical Chemistry Local-density approximation Inorganic compound
Zdroj:	Inorganic Chemistry. 25:3876-3879
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic00242a009
Popis:	A detailed theoretical analysis is presented of the similarities and differences of the electronic structures of Mo/sub 2/O/sub 2/(..mu..-S)/sub 2/(S/sub 2/)/sub 2//sup 2 -/ (1) and Mo/sub 2/S/sub 2/(..mu..-S)/sub 2/(S/sub 2/)/sub 2//sup 2 -/ (2). The analysis is based on self-consistent, first-principles electronic structure calculations for both systems. The replacement of the O atoms in 1 with S atoms in 2 leaves the higher filled MOs unaffected, although it removes the lower lying molecular orbitals corresponding to the Mo-O triple bond. The LUMOs, which in 1 are the Mo-O antibonding orbitals, are in 2 the Mo-S(terminal) antibonding orbitals at lower energies, decreasing the LUMO-HOMO gap in accordance with experimental observations. The energies of other antibonding orbitals are shifted somewhat to lower energies in going from 1 to 2. The results suggest a similar reactivity pattern for reactions involving primarily the HOMO S/sub 2/ ..pi.. orbitals, i.e., reactions with electrophiles. For reactions with nucleophilic components, somewhat lower activation energies should be expected due to the lowering of the HOMO-LUMO gap in 2 compared to that in 1.
Databáze:	OpenAIRE
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