A1 Journal article (refereed)
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” (2021)


Stennett, C. R., Wagner, C. L., Fettinger, J. C., Vasko, P., & Power, P. P. (2021). 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”. Inorganic Chemistry, 60(15), 11401-11411. https://doi.org/10.1021/acs.inorgchem.1c01399


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Publication details

All authors or editors: Stennett, Cary R.; Wagner, Clifton L.; Fettinger, James C.; Vasko, Petra; Power, Philip P.

Journal or series: Inorganic Chemistry

ISSN: 0020-1669

eISSN: 1520-510X

Publication year: 2021

Volume: 60

Issue number: 15

Pages range: 11401-11411

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.inorgchem.1c01399

Publication open access: Not open

Publication channel open access:


Abstract

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.


Keywords: coordination complexes; organometallic compounds; vanadium; chromium; iron; hydrides


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Last updated on 2021-09-08 at 13:41