UPS Study of Compounds with Metal−Silicon Bonds: M(CO)nSiCl3 (M = Co, Mn; n = 4, 5) and Fe(CO)4(SiCl3)2
| Autor: | Lan Luo, How Ghee Ang, Wei Huang, Hsing Hua Huang, Igor Novak, Christian Erich Zybill |
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| Rok vydání: | 1997 |
| Předmět: |
Silicon
Chemistry Organic Chemistry Solid-state chemistry.chemical_element Metal carbonyl Bond-dissociation energy Spectral line Inorganic Chemistry Metal Crystallography visual_art visual_art.visual_art_medium Density functional theory Physical and Theoretical Chemistry Polarization (electrochemistry) |
| Zdroj: | Organometallics. 16:1567-1572 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om960692t |
| Popis: | The (trichlorosilyl) (and -germyl)metal carbonyls Co(CO)4SiCl3, Co(CO)4GeCl3, Mn(CO)5SiCl3, and cis-Fe(CO)4(SiCl3)2 have been synthesized in high yields. He I photoelectron spectra (UPS) of the complexes have been measured and interpreted on the basis of empirical arguments and density functional theory (DFT) calculations. For cis/trans-Fe(CO)4(SiCl3)2 isomers the calculations predict the trans-isomer to be more stable than cis by 15.2 kJ mol-1. The cis-isomer is exclusively present in the solid state and in the gas phase. UPS results suggest the importance of charge polarization effects and the lack of π-back-donation along TM−Si bonds. The calculated M−Si bond distances amounted to 2.34 A (Co−Si), 2.43 A (Co−Ge), 2.47 A (Mn−Si), 2.41 A (trans-Fe−Si), and 2.45 A (cis-Fe−Si). For Co(CO)4SiCl3, the DFT calculated Co−Si bond dissociation energy was 317.7 kJ mol-1, compared to 222.2 kJ mol-1 for Co−C energy in Co(CO)4CCl3. |
| Databáze: | OpenAIRE |
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