Wydział Chemii

Barbara Machura

M. Wolff

I. Gryca

Jerzy Mroziński

2011

Polyhedron

30

354-363

10.1016/j.poly.2010.10.025

Naukowa

Angielski

Artykuł

The reaction of [ReO(OMe)Cl₂(dpphen)] (dpphen = 4,7-diphenyl-1,10-phenanthroline) with triphenylphosphine has been examined and two novel rhenium complexes – [Re^IIICl₃(dpphen)(PPh₃)]·Me₂CO (1) and [Re^IVCl₄(dpphen)]·CHCl₃ (2) – have been obtained. The compounds have been characterised by elemental analysis, IR, UV–Vis spectroscopy, magnetic measurements and X-ray crystallography. The electronic structures of [ReCl₃(dpphen)(PPh₃)] and [ReCl₄(dpphen)] have been studied by DFT/B3LYP level calculations, and TD-DFT calculations have been employed for discussion of the electronic spectra in more detail. The magnetic behaviour of 1 is characteristic of mononuclear complexes with d⁴ low-spin octahedral Re(III) complexes (³T_1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives diamagnetic ground state. For complex 2 the results of calculations revealed value of zero-field splitting parameter D = 10.8 cm⁻¹, g_|| = 2.49 and g_⊥ = 1.51

Re(III) and Re(IV) complexes, lanthanides, 7-diphenyl-1, 10-phenanthroline, X-ray structure, Electronic structure, DFT calculation

https://doi.org/10.1016/j.poly.2010.10.025

http://www.elsevier.com