Wydział Chemii

Magdalena Stosur

Andrzej Kochel

Antoni Keller

Teresa Szymańska-Buzar

2006

Organometallics

25

3791-3794

10.1021/om060290d

Naukowa

Angielski

Artykuł

Photolysis of Mo(CO)₆ in n-heptane solution creates a coordinatively unsaturated d⁶ species, which interacts with the Si−H bond of Et₂SiH₂ and leads to the formation of Mo−H and Mo−Si bonds. The formation of a Mo−H bond was corroborated by ¹H NMR spectroscopy due to the detection of a high-field resonance at δ = −8.33 flanked by ²⁹Si satellites. The formation of Mo−Si bonds was confirmed by the detection of two sets of ²⁹Si satellites on the hydride signal, which provided J_Si-H = 57 and 33 Hz, and by the ²⁹Si{¹H} NMR spectrum, which revealed a resonance at δ = 207.7. The latter signal in the ²⁹Si NMR spectrum was observed as a doublet of quintets with ¹J_Si-H = 58 Hz and ²J_Si-H = 41 Hz. The ⁹⁵Mo NMR spectrum showed at high field a resonance at δ = −3785, characteristic for seven-coordinate molybdenum compounds. The molecular structure of a novel bis{(μ η²-hydridodiethylsilyl)tetracarbonylmolybdenum(I)} complex, [{Mo(μ-η²-H−SiEt₂)(CO)₄}₂], was established by single-crystal X-ray diffraction studies. The molybdenum hydride observed in the ¹H NMR spectrum was located in the structure at a chemically reasonable position between the Mo and Si atoms of the Mo−Si bonds of the bridging silyl ligand with a Si−H bond length of 1.615(3) Å and that of the Mo−H bond amounting to 1.786(5) Å.

Silicon, Anions, Ligands, Molybdenum, Resonance structures

https://doi.org/10.1021/om060290d

https://www.acs.org/content/acs/en.html