Formation of Ammonia from an Iron Nitrido Complex

Scepaniak, Jeremiah J.; Young, Jessica; Bontchev, Ranko P.; Smith, Jeremy M.

doi:10.1002/anie.200900381

Cited by 213 publications

(187 citation statements)

References 38 publications

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“…The sodium salt of TEMPO was prepared and isolated according to the literature. 9 It was subsequently treated with triethylamine hydrochloride, producing 1 in approximately 54% yield.…”

Section: Resultsmentioning

confidence: 99%

Anhydrous TEMPO-H: reactions of a good hydrogen atom donor with low-valent carbon centres

et al. 2011

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In this paper, we report a novel synthesis of anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H). An X-ray crystal structure and full characterization of the compound are included. Compared to hydrated TEMPO-H, its anhydrous form exhibits improved stability and a differing chemical reactivity. The reactions of anhydrous TEMPO-H with a variety of low-valent carbon centres are described. For example, anhydrous TEMPO-H was reacted with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), an unsaturated NHC. Crystals of [CHNC 6 H 2 (CH 3 ) 3 ] 2 C ◊ ◊ ◊ HO-(NC 5 H 6 (CH 3 ) 4 ), IMes ◊ ◊ ◊ TEMPO-H, were isolated and a crystal structure determined. The experimental structure is compared to the results of theoretical calculations on the hydrogen-bonded dimer. Anhydrous TEMPO-H was also reacted with the saturated NHC, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), giving the product [CH 2 Ni-Pr 2 C 6 H 3 ] 2 CH ◊ ◊ ◊ O(NC 5 H 6 (CH 3 ) 4 ). In contrast, the reaction of hydrated TEMPO-H with 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene gave small amounts of the hydrolysis product, N-(2,6-diisopropylphenyl)-N- [2-(2,6-diisopropylphenylamino)ethyl]formamide. Finally, anhydrous TEMPO-H was reacted with (triphenylphosphoranylidene)ketene to generate Ph 3 PC(H)C( O)O(NC 5 H 6 (CH 3 ) 4 ). A full characterization of the product, including an X-ray crystal structure, is described. Scheme 1 Structural isomers formed by the reaction of TEMPO-H (1) with NHCs (2).Access to anhydrous TEMPO-H has not been reported in the literature, but it was clear to us early on that the water in

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“…The sodium salt of TEMPO was prepared and isolated according to the literature. 9 It was subsequently treated with triethylamine hydrochloride, producing 1 in approximately 54% yield.…”

Section: Resultsmentioning

confidence: 99%

Anhydrous TEMPO-H: reactions of a good hydrogen atom donor with low-valent carbon centres

et al. 2011

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“…Accordingly, Smith and coworkers have prepared a range of novel transition metal nitride complexes [102], some of which may represent key intermediates in the catalytic cycle of the nitrogenase enzyme. Significantly, the iron (IV) nitrido complex {PhB(MesIm) 3 }FeN releases ammonia upon reaction with a hydrogen-atom donor [103]. Subsequently, the same researchers isolated and structurally characterized the remarkable cationic iron(V) nitrido complex [{PhB(…”

Section: Tris(carbene)boratesmentioning

confidence: 99%

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

Rabinovich

2016

Structure and Bonding

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The coordination chemistry of scorpionates, anionic tripodal boroncentered ligands that readily bind to virtually all main group, transition, and f-block metals, has had a profound effect in the development of synthetic bioinorganic chemistry during the past 50 years. Highlighted in this article are some of the most meaningful results published in the area, primarily in the preparation of structural and functional model compounds for the active sites in metalloproteins and metalloenzymes, a theme that encompasses topics as diverse as nitrogen fixation and heavy metal poisoning. It has also been 50 years since the genesis of Structure and Bonding, so let this account also be a celebration of the many contributions that the staunch serial has had on the entire field of inorganic chemistry during the past half century.

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“…Recent reports evidenced the potential of isolated and putative nitrido complexes in intramolecular C-H [11] and dihydrogen [7,8] activation. Further prominent reactions include an hydrogen atom abstraction, [12] the dimerization to dinitrogen complexes, [13] nitrogen transfer, [14,15] and the reactions with the nucleophiles Me 3 NO [8,10] and Ph 3 P. [4,15] For the later reaction Smith et al have recently shown, that both, electron donation to and from the nitrido nitrogen atom take place in the transition state. [16] Recently, we have shown that square-planar iridium complexes with a terminal nitrido unit also react with silanes under insertion of the nitrido nitrogen atom into the Si-H bond.…”

Section: Introductionmentioning

confidence: 97%