Reductive silylation of molecular nitrogen via fixation to tris(trialkylsilyl)amine

Shiina, Kyo

doi:10.1021/ja00781a068

Cited by 119 publications

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“…Catalytic reductive silylation of N2 was pioneered by Shiina who used CrCl3 as the pre-catalyst. This led to formation of 5.4 equivalents of N(SiMe3)3 when N2 was reacted with lithium and Me3SiCl [24]. Other salts of various metals yielded much less of the desired product.…”

Section: Introductionmentioning

confidence: 99%

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Dzik

2016

Inorganics

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Abstract:Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh 3 ) 3 N 2 are presented. We show that in the presence of the title compound, the reaction of N 2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilyl)amine per Co atom in THF (tetrahydrofuran). The aim was to elucidate whether the active catalyst is: (a) the [Co(PPh 3 ) 3 N 2 ]´anion formed after two-electron reduction of the title compound; or (b) a species formed via decomposition of CoH(PPh 3 ) 3 N 2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst.

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Section: Introductionmentioning

confidence: 99%

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Dzik

2016

Inorganics

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“…[26] For comparison, we also explored (CAAC) 2 Fe in the context of catalytic N 2 silylation. Catalytic silylation reactions of N 2 under strongly reducing conditions have been known for many years using metals such as Cr, [27] Ti [28] and Mo, [29] and recently, such silylations were extended to systems using Fe pre-catalysts including Fe(CO) 5 and Cp 2 Fe. [30] For example, Fe(CO) 5 was shown to produce up to 25 equivalents of N(SiMe 3 ) 3 per Fe in the presence of a vast excess sodium metal and TMSCl at room temperature.…”

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confidence: 99%

Low‐Temperature N₂ Binding to Two‐Coordinate L₂Fe⁰ Enables Reductive Trapping of L₂FeN₂⁻ and NH₃ Generation

Ung

Peters

2014

Angewandte Chemie

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The 2-coordinate (CAAC) 2 Fe complex [CAAC = cyclic (alkyl)(amino)carbene] binds dinitrogen at low temperature (T < −80 °C). The resulting putative 3-coordinate N 2 -complex, (CAAC) 2 Fe(N 2 ), was trapped by one electron reduction to its corresponding anion [(CAAC) 2 FeN 2 ] − at low temperature. This complex was structurally characterized and features an activated dinitrogen unit that can be silylated at the β-nitrogen. KeywordsIron; Nitrogen fixation; Low-coordinate; Carbenes While hundreds of transition-metal-N 2 complexes have been prepared and studied, [1] comparatively few systems afford access to productive N 2 functionalization. [2] This is particularly true for the case of N 2 functionalization by protons and electrons to produce NH 3 (or N 2 H 4 ). Building on extensive early Mo and W model work, [3] Schrock [4] and Nishibayashi [5] have reported Mo-containing coordination complexes (A and B in Figure 1, respectively) that facilitate catalytic N 2 reduction to NH 3 in the presence of suitable acids and reductants. Because Fe is (i) the only transition metal known to be essential to enzymatic nitrogenase function, [6] and (ii) the predominant transition metal catalyst used in the Haber-Bosch ammonia synthesis, [7] studying N 2 reduction chemistry at well-defined Fe model complexes is of interest. [8,9] Recently, our lab demonstrated that Fe coordination complexes (C in Figure 1) are capable of modest catalytic N 2 reduction to NH 3 . [10] ** This work was supported by the N.I.H. (GM 070757) and the Gordon and Betty Moore Foundation. We thank Larry Henling and Michael K. Takase for crystallographic assistance.

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“…The first example of the catalytic formation of 1 was reported for the reaction of N 2 with Li as a reducing agent and Me 3 SiCl in the presence of various metal salts, such as CrCl 3 as catalysts, where up to 5.4 equiv. of 1 was produced based on the catalyst 10 . In this reaction system, the possibility of the formation of lithium nitride (Li 3 N) as a reactive intermediate cannot be completely excluded (similarly, Mori 11 also reported the transformation of N 2 using Li as a reducing agent in the presence of Ti complexes).…”

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Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

et al. 2012

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Reductive silylation of molecular nitrogen via fixation to tris(trialkylsilyl)amine

Cited by 119 publications

References 1 publication

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Low‐Temperature N₂ Binding to Two‐Coordinate L₂Fe⁰ Enables Reductive Trapping of L₂FeN₂⁻ and NH₃ Generation

Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

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Reductive silylation of molecular nitrogen via fixation to tris(trialkylsilyl)amine

Cited by 119 publications

References 1 publication

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(Triphenylphosphine)Cobalt(I)

Low‐Temperature N2 Binding to Two‐Coordinate L2Fe0 Enables Reductive Trapping of L2FeN2− and NH3 Generation

Iron-catalysed transformation of molecular dinitrogen into silylamine under ambient conditions

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Low‐Temperature N₂ Binding to Two‐Coordinate L₂Fe⁰ Enables Reductive Trapping of L₂FeN₂⁻ and NH₃ Generation