Aluminum-Stabilized Low-Spin Iron(II) Hydrido Complexes of 1,4,7-Trimethyl-1,4,7-triazacyclononane

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• 作者：Masataka Oishi ; Togo Endo ; Masato Oshima ; Hiroharu Suzuki
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：May 19, 2014
• 年：2014
• 卷：53
• 期：10
• 页码：5100-5108
• 全文大小：463K
• 年卷期：v.53,no.10(May 19, 2014)
• ISSN：1520-510X

文摘

We investigated herein the reactions of (Me₃tacn)FeCl_n (1a: n = 3, 1b: n = 2) with common aluminum hydride reagents and a bulky dihydridoaluminate {Li(ether)₂}{Al(OC₆H₃-2,6-^tBu₂)}(渭-H)₂, which yielded the diamagnetic hydrido complexes 2鈥?b>4 containing Fe(II) and Al(III). In particular, the use of divalent 1b afforded excellent isolated yields. The structures of 2鈥?b>4 were determined using spectroscopic and crystallographic analyses. The crystal structures showed distorted octahedral Fe centers and fairly short Fe鈥揂l distances [2.19鈥?.24 脜]. The structures of cation moiety 2 and neutral complex 4 were further probed using DFT calculations, which indicated a stable low-spin Fe(II) state and strongly electron-donating nature of the (Me₃tacn)FeH₃ fragment toward the Al(III) center.