Reductions of M{N(SiMe3)2}3 (M = V, Cr, Fe): Terminal and Bridging Low-Valent First-Row Transition Metal Hydrido Complexes and 'Metallo-Transamination'
| Autor: | Cary R. Stennett, Philip P. Power, Clifton L. Wagner, Petra Vasko, James C. Fettinger |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Hydride Vanadium chemistry.chemical_element Trimethylamine 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Metal chemistry.chemical_compound Crystallography chemistry Transition metal visual_art visual_art.visual_art_medium Lithium Physical and Theoretical Chemistry Diethyl ether Crown ether |
| Zdroj: | Inorganic Chemistry. 60:11401-11411 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The reaction of the vanadium(III) tris(silylamide) V{N(SiMe3)2}3 with LiAlH4 in diethyl ether gives the highly unstable mixed-metal polyhydride [V(μ2-H)6[Al{N(SiMe3)2}2]3][Li(OEt2)3] (1), which was structurally characterized. Alternatively, performing the same reaction in the presence of 12-crown-4 affords a rare example of a structurally verified vanadium terminal hydride complex, [VH{N(SiMe3)2}3][Li(12-crown-4)2] (2). The corresponding deuteride 2D was also prepared using LiAlD4. In contrast, no hydride complexes were isolated by reaction of M{N(SiMe3)2}3 (M = Cr, Fe) with LiAlH4 and 12-crown-4. Instead, these reactions afforded the anionic metal(II) complexes [M{N(SiMe3)2}3][Li(12-crown-4)2] (3, M = Cr; 4, M = Fe). The reaction of the iron(III) tris(silylamide) Fe{N(SiMe3)2}3 with lithium aluminum hydride without a crown ether gives the "hydrido inverse crown" complex [Fe(μ2-H){N(SiMe3)2}2(μ2-Li)]2 (5), while treatment of the same trisamide with alane trimethylamine complex gives the iron(II) polyhydride complex Fe(μ2-H)6[Al{N(SiMe3)2}2]2[Al{N(SiMe3)2}(NMe3)] (6). Complexes 2-6 were characterized by X-ray crystallography, as well as by infrared, electronic, and 1H and 13C (complex 6) NMR spectroscopies. Complexes 1 and 6 are apparently formed by an unusual "metallo-transamination" process. |
| Databáze: | OpenAIRE |
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