Molecular and electronic structures of germylene and stannylene complexes (CO)5MECl2·nTHF (M = Cr, W; E = Ge, Sn; n = 1, 2) as studied by IR and Raman spectroscopy, X-ray analysis, and quantum chemistry

• Published in: Russian chemical bulletin 2010-02, Vol.59 (2), p.348-360
• Main Authors: Aysin, R. R., Koroteev, P. S., Korlyukov, A. A., Zabula, A. V., Bukalov, S. S., Leites, L. A., Egorov, M. P., Nefedov, O. M.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Articles; Inorganic Chemistry; Organic Chemistry
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-010-0086-3

The Raman and IR spectra of the complexes (CO) 5 CrSnCl 2 ·THF ( 1 ), (CO) 5 WSnCl 2 ·THF ( 2 ), (CO) 5 CrGeCl 2 ·THF ( 3 ), (CO) 5 WGeCl 2 ·THF ( 4 ), (CO) 5 CrSnCl 2 ·2THF ( 5 ), and (CO) 5 WSnCl 2 ·2THF ( 6 ) were measured and interpreted using quantum chemical calculations. Complexes 3 and 5 were characterized by X-ray analysis. The stretching vibrations of the CO groups in the spectra of solutions of complexes 1–6 obey the selection rules for C 4 ν local symmetry. For the complexes containing 0 (type A), 1 (type B), and 2 (type C) THF molecules, a comparison was made of the calculated and experimental M E II bond lengths and energies, as well as the ν(CO) vibrational frequencies. The contribution of the π-component to the M E II bond decreases in the order A→B→C and leads to enhancement of the donor ability of the carbene-like ligand and to a slight elongation and weakening of this bond. An attempt to grow crystals of complex 6 in air unexpectedly resulted in a polynuclear complex [(CO) 5 WSn(Cl)(μ-OH) 2 SnCl 2 (μ-OH)] 2 ·6THF, which was characterized by X-ray analysis and Raman spectroscopy.