Stabilization of Low Valent Silicon Fluorides in the Coordination Sphere of Transition Metals
| Autor: | Dietmar Stalke, Hilke Wolf, Herbert W. Roesky, Ramachandran Azhakar, Rajendra S. Ghadwal |
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| Rok vydání: | 2012 |
| Předmět: |
Models
Molecular Coordination sphere Silicon Inorganic chemistry chemistry.chemical_element Crystallography X-Ray 010402 general chemistry 01 natural sciences Biochemistry Chloride Catalysis Fluorides chemistry.chemical_compound Colloid and Surface Chemistry Transition metal Organometallic Compounds Transition Elements medicine Inert gas Molecular Structure 010405 organic chemistry Silicon Compounds General Chemistry Nuclear magnetic resonance spectroscopy Oxidative addition 0104 chemical sciences chemistry Fluoride medicine.drug |
| Zdroj: | Journal of the American Chemical Society. 134:2423-2428 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja210697p |
| Popis: | Silicon(II) fluoride is unstable; therefore, isolation of the stable species is highly challenging and was not successful during the last 45 years. SiF(2) is generally generated in the gas phase at very high temperatures (~1100-1200 °C) and low pressures and readily disproportionates or polymerizes. We accomplished the syntheses of stable silicon(II) fluoride species by coordination of silicon(II) to transition metal carbonyls. Silicon(II) fluoride compounds L(F)Si·M(CO)(5) {M = Cr (4), Mo (5), W(6)} (L = PhC(NtBu)(2)) were prepared by metathesis reaction from the corresponding chloride with Me(3)SnF. However, the chloride derivatives L(Cl)Si·M(CO)(5) {M = Cr (1), Mo (2), W(3)} (L = PhC(NtBu)(2)) were prepared by the treatment of transition metal carbonyls with L(Cl)Si. Direct fluorination of L(Cl)Si with Me(3)SnF resulted in oxidative addition products. Compounds 4-6 are stable at ambient temperature under an inert atmosphere of nitrogen. Compounds 4-6 were characterized by NMR spectroscopy, EI-MS spectrometry, and elemental analysis. The molecular structures of 4 and 6 were unambiguously established by single-crystal X-ray diffraction. Compounds 4 and 6 are the first structurally characterized fluorides, after the discovery of SiF(2) about four and a half decades ago. |
| Databáze: | OpenAIRE |
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