Wydział Chemii

Jarosław Handzlik

Andrzej Kochel

Teresa Szymańska-Buzar

2012

Polyhedron

31

622-631

10.1016/j.poly.2011.10.040

Naukowa

Angielski

Artykuł

The activation of the Ge–H bond and the formation of several hydride complexes, characterized by high-field resonances, have been detected during the ¹H NMR spectroscopy monitoring of the photochemical reaction of Et₃GeH and Et₂GeH₂ with W(CO)₆ and the norbornadiene complex [W(CO)₄(η⁴-nbd)]. The activation of the Ge–H bond of triethylgermane in the photochemical reactions of tungsten(0) complexes has been applied in the hydrogermylation of norbornadiene (nbd), which leads to the formation of endo-triethylgermylnorbornene as the major product. The complex [{W(μ-η²-H–GeEt₂)(CO)₄}₂] has been fully characterized by NMR spectroscopy and by a single-crystal X-ray diffraction study. Evidence for the hydride ligand of the W(μ-η²-H–GeEt₂) group has been provided by ¹H NMR spectroscopy (δ = −9.02, ¹J_H–W = 31 Hz) and by DFT calculations. A DFT study of the structural properties and ¹H NMR chemical shifts of several possible intermediate σ and hydride complexes formed during the photochemical reaction of W(CO)₆ and Et₂GeH₂ has been performed.

Tungsten, Germane, σ-Bond activation, Hydrogermylation, Photolysis, DFT calculation

https://doi.org/10.1016/j.poly.2011.10.040

http://www.elsevier.com