Reduction of (tBuN鈺?NbCl3(py)2 in a Salt-Free Manner for Generating Nb(IV) Dinuclear Complexes and Their Reactivity toward Benzo[c]cinnoline

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• 作者：Teruhiko Saito ; Haruka Nishiyama ; Kento Kawakita ; Michael Nechayev ; Benjamin Kriegel ; Hayato Tsurugi ; John Arnold ; Kazushi Mashima
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：June 15, 2015
• 年：2015
• 卷：54
• 期：12
• 页码：6004-6009
• 全文大小：353K
• ISSN：1520-510X

文摘

The organosilicon reducing reagent 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (1a) was used for the one-electron, salt-free reduction of (^tBuN鈺?NbCl₃(py)₂ (2), resulting in the formation of a neutral, triply chloride-bridged dinuclear niobium(IV) complex, [(^tBuN鈺?ClNb(py)](渭-Cl)₃[(^tBuN鈺?Nb(py)₂] (3) in moderately high yield. Heating 3 in toluene at 80 掳C caused a unique intramolecular rearrangement of 3 to another neutral dinuclear complex, [Cl₂Nb(py)](渭-Cl)(渭-N^tBu)₂[ClNb(py)₂] (4), in which two niobium(IV) atoms were bridged by one chloride atom and two imido ligands. Reaction of complex 3 with benzo[c]cinnoline produced a benzo[c]cinnoline-bridged dinuclear niobium(V) complex 7 by an overall two-electron reduction of benzo[c]cinnoline through a disproportionation of 3 into a mixture of a niobium(V) complex 2 and a niobium(III) complex, the latter of which efficiently reduced benzo[c]cinnoline.