Electronic structure of rhodium( II ) dimers of formula [Rh 2 X 2 (µ-O 2 CH) 2 (HNCHCHNH) 2 ](X = halide)

1994; Royal Society of Chemistry; Issue: 22 Linguagem: Inglês

10.1039/dt9940003261

ISSN

2050-5671

Autores

Leszek Natkaniec, Florian P. Pruchnik,

Tópico(s)

Metal complexes synthesis and properties

Resumo

The electronic structures of the dirhodium complexes [Rh2(µ-O2CH)4(H2O)2] and [Rh2X2(µ-O2CH)2(HNCHCHNH)2](X = Cl, Br or I) have been calculated by the Fenske–Hall method. The calculations gave the electronic configurations σ2π4δ2δ*2π*4σ* with σ* as the lowest unoccupied molecular orbital for [Rh2(µ-O2CH)4(H2O)2] and highest occupied molecular orbital < 18a1, 16b1(π* HNCHCHNH) < 17b1(σ*) for [Rh2X2(µ-O2CH)2(HNCHCHNH)2]. All Rh–Rh orbitale of the latter complexes have considerably higher ligand contributions than those of [Rh2(O2CH)4(H2O)2]. The strength of the Rh–Rh bond and the electronic spectra of the complexes are discussed.

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