Photochemical Reaction of Mo(CO)6 with Et2SiH2: Spectroscopic Characterization and Crystal Structure of the Bis{(<img src="http://pubs.acs.org/images/entities/mgr.g
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- 作者：Magdalena Stosur ; Andrzej Kochel ; Antoni Keller ; and Teresa Szyma<img src="http ; //pubs.acs.org/images/entities/nacute.gif" border="0">ska-Buzar
- 刊名：Organometallics
- 出版年：2006
- 出版时间：July 17, 2006
- 年：2006
- 卷：25
- 期：15
- 页码：3791 - 3794
- 全文大小：69K
- 年卷期：v.25,no.15(July 17, 2006)
- ISSN：1520-6041
文摘
Photolysis of Mo(CO)6 in n-heptane solution createsa coordinatively unsaturated d6 species, which interacts withthe Si-H bond of Et2SiH2 and leads to the formation of Mo-Hand Mo-Si bonds. The formation of a Mo-H bond wascorroborated by 1H NMR spectroscopy due to the detection ofa high-field resonance at <IMG SRC="/images/gifchars/delta.gif" BORDER=0 > = -8.33 flanked by 29Si satellites.The formation of Mo-Si bonds was confirmed by the detectionof two sets of 29Si satellites on the hydride signal, whichprovided JSi-H = 57 and 33 Hz, and by the 29Si{1H} NMRspectrum, which revealed a resonance at 
= 207.7. The lattersignal in the 29Si NMR spectrum was observed as a doublet ofquintets with 1JSi-H = 58 Hz and 2JSi-H = 41 Hz. The 95MoNMR spectrum showed at high field a resonance at = -3785,characteristic for seven-coordinate molybdenum compounds.The molecular structure of a novel bis{(
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2-hydridodiethylsilyl)tetracarbonylmolybdenum(I)} complex, [{Mo(-2-H-SiEt2)(CO)4}2], was established by single-crystal X-ray diffraction studies. The molybdenum hydride observed in the 1H NMRspectrum was located in the structure at a chemically reasonableposition between the Mo and Si atoms of the Mo-Si bonds ofthe 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.
= 207.7. The lattersignal in the 29Si NMR spectrum was observed as a doublet ofquintets with 1JSi-H = 58 Hz and 2JSi-H = 41 Hz. The 95MoNMR spectrum showed at high field a resonance at = -3785,characteristic for seven-coordinate molybdenum compounds.The molecular structure of a novel bis{(-2-hydridodiethylsilyl)tetracarbonylmolybdenum(I)} complex, [{Mo(-2-H-SiEt2)(CO)4}2], was established by single-crystal X-ray diffraction studies. The molybdenum hydride observed in the 1H NMRspectrum was located in the structure at a chemically reasonableposition between the Mo and Si atoms of the Mo-Si bonds ofthe 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.