Photochemical Reaction of Mo(CO)6 with Et2SiH2: Spectroscopic Characterization and Crystal Structure of the Bis{(μ-η2-hydridodiethylsilyl)tetracarbonylmolybdenum(I)} Complex [{Mo(μ-η2-H−SiEt2)(CO)4}2

Abstract

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 JSi-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 1JSi-H = 58 Hz and 2JSi-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 mol...