Application of the molybdenum(IV) hydride complexes in cyclohexane solutions to the radiation-catalytic reduction of molecular nitrogen

Dziegielewski, J. O.; Grzybek, R.

doi:10.1016/s0277-5387(00)80270-3

Cited by 18 publications

(4 citation statements)

References 17 publications

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“…To date, well-defined transition-metal hydride complexes that enable N 2 cleavage and hydrogenation have been limited only to group 4 and 5 transition metals. Some group 6 transition-metal chromium , and molybdenum − hydride complexes are known to trap N 2 , but significant reduction of a coordinated N 2 unit has not been observed. − Beyond group 6 transition metals, several hydride complexes with weakly coordinated N 2 units have been reported. − …”

Section: Introductionmentioning

confidence: 99%

Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes

et al. 2020

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Activation of dinitrogen (N2) by well-defined metal hydrides is of much interest and importance, but studies in this area have remained limited to date. We report here N2 activation and hydrogenation by C5Me4SiMe3-ligated di- and trinuclear chromium polyhydride complexes. Hydrogenolysis of [Cp′Cr(μ-Me)2CrCp′] (Cp′ = C5Me4SiMe3) (1) with H2 in a dilute hexane solution under N2-free conditions affords the dichromium dihydride complex [Cp′Cr(μ-H)2CrCp′] (2), while hydrogenolysis of 1 in a concentrated solution or without solvent provides the trinuclear chromium tetrahydride complex [(Cp′Cr)3(μ3-H)(μ-H)3] (3). When the reaction is carried out in the presence of N2 in a dilute hexane solution, the tetranuclear diimide/dihydride complex [(Cp′Cr)4(μ3-NH)2(μ3-H)2] (4) is formed via N–N bond cleavage and N–H bond formation. The reaction of 2 with N2 at room temperature gives the tetranuclear imide/nitride/dihydride complex [(Cp′Cr)3(C5Me3(CH2)SiMe3)Cr(μ3-NH)(μ3-N)(μ-H)2] (5) via N2 cleavage and hydrogenation and C–H bond activation of a Cp methyl group. At –30 °C, the reaction of 2 with N2 affords the dinitride intermediate [(Cp′Cr)4(μ3-N)2(μ3-H)2] (6), which is quantitatively transformed to 5 at room temperature. Complex 5 reversibly converts to the stereoisomer 5′. The hydrogenation of a mixture of 5 and 5′ with H2 affords 4. The reaction of 3 with N2 proceeds at 100 °C to afford [(Cp′Cr)3(μ3-NH)2] (7). This transformation has also been investigated by DFT calculations. Both experimental and computational studies suggest that N2 incorporation into the chromium hydride cluster is involved in the rate-determining step. This work represents the first example of N2 cleavage and hydrogenation by well-defined chromium hydride complexes.

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Section: Introductionmentioning

confidence: 99%

Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes

et al. 2020

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“…Reduction of Mo-Cl with Mg in THF under a dinitrogen atmosphere produces crude "Mo-NdN-Mg(THF) 3 Cl", which upon recrystallization from pentane yields red, diamagnetic Mo-NdN-MgCl(THF) 3 (in Nujol ν NN ) 1810 cm -1 , ν15 N 15 N ) 1751 cm -1 ; in C 6 D 6 ν NN ) 1812 cm -1 ; Scheme 2). If the Mg reduction is followed by treatment with Bu 4 NCl and dioxane, bright green, benzene-soluble, diamagnetic {Bu 4 N}{Mo-NdN} is formed (in THF ν NN ) 1859 cm -1 , ν15 N 15 N ) 1794 cm -1 ).…”

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confidence: 99%

“…Over 30 years of research have been devoted to the synthesis and study of transition-metal complexes that contain dinitrogen − and in no instance is the catalyst a “well-defined” species. With that goal in mind we have chosen to explore the chemistry of triamidoamine ([(RNCH 2 CH 2 ) 3 N] 3- = [RN 3 N] 3- ) molybdenum complexes, especially those in which R is an ordinary aryl group , (cf.…”

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confidence: 99%

Reduction of Dinitrogen to Ammonia at a Well-Protected Reaction Site in a Molybdenum Triamidoamine Complex

2002

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We have synthesized a triamidoamine ligand ([(RNCH2CH2)3N]3-) in which R is 3,5-(2,4,6-i-Pr3C6H2)2C6H3 (HexaIsoPropylTerphenyl or HIPT). The reaction between MoCl4(THF)2 and H3[HIPTN3N] in THF followed by 3.1 equiv of LiN(SiMe3)2 led to formation of orange [HIPTN3N]MoCl. Reduction of [HIPTN3N]MoCl with magnesium in THF under dinitrogen led to formation of salts that contain the {[HIPTN3N]Mo(N2)}- ion. The {[HIPTN3N]Mo(N2)}- ion can be oxidized by zinc chloride to give [HIPTN3N]Mo(N2) or protonated to give [HIPTN3N]Mo-N=N-H. Other relevant compounds that have been prepared include {[HIPTN3N]Mo-N=NH2}+, [HIPTN3N]MoN, {[HIPTN3N]Mo=NH}+, and {[HIPTN3N]Mo(NH3)}+. (The anion is usually {B(3,5-(CF3)2C6H3)4}- = {BAr'4}-.) Reduction of [HIPTN3N]Mo(N2) with CoCp2 in the presence of {2,6-lutidinium}BAr'4 in benzene leads to formation of ammonia and {[HIPTN3N]Mo(NH3)}+. Preliminary X-ray studies suggest that the HIPT substituent creates a deep, three-fold symmetric cavity that protects a variety of dinitrogen reduction products against bimolecular decomposition reactions, while at the same time the metal is left relatively open toward reactions near the equatorial amido ligands.

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“…Although ammonia (NH 3 ) is currently synthesized from nitrogen (N 2 ) and hydrogen (H 2 ) at high temperature (500 • C) and high pressure (above 200 atm) with iron catalysts, a biological nitrogen-fixation system can operate under mild conditions [1][2][3][4]. A few research groups reported nonbiological catalytic reduction of nitrogen to ammonia at ambient temperature and pressure with catalysts including metal centers [5][6][7][8][9]. On the other hand, some studies have reported the production of NH 3 from nitrogen and hydrogen using non-equilibrium plasmas at low pressure [10][11][12][13][14], or atmospheric pressure [15,16].…”

Section: Synthesis Of Ammonia Through Direct Chemical Reactions Betwementioning

confidence: 99%

Synthesis of Ammonia through Direct Chemical Reactions between an Atmospheric Nitrogen Plasma Jet and a Liquid

Kubota

Koga

Ohno

et al. 2010

Plasma and Fusion Research

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Fundamental chemical reactions between an atmospheric nitrogen plasma jet and water or a water/ethanol solution have been investigated. When the nitrogen plasma jet was injected directly into pure water, active nitrogen species produced nitric acid and ammonia through fatal reactions with H 2 O. The interaction between nitrogen plasma and a liquid mixture of pure water and ethanol produced NH 4 + ions effectively. These experimental results clearly show that the active nitrogen species in the pulsed-discharge atmospheric plasma can interact strongly with materials in solution to extract oxygen or hydrogen from them and add atomic nitrogen to them.

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Application of the molybdenum(IV) hydride complexes in cyclohexane solutions to the radiation-catalytic reduction of molecular nitrogen

Cited by 18 publications

References 17 publications

Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes

Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes

Reduction of Dinitrogen to Ammonia at a Well-Protected Reaction Site in a Molybdenum Triamidoamine Complex

Synthesis of Ammonia through Direct Chemical Reactions between an Atmospheric Nitrogen Plasma Jet and a Liquid

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Application of the molybdenum(IV) hydride complexes in cyclohexane solutions to the radiation-catalytic reduction of molecular nitrogen

Cited by 18 publications

References 17 publications

Dinitrogen Activation and Hydrogenation by C5Me4SiMe3-Ligated Di- and Trinuclear Chromium Hydride Complexes

Dinitrogen Activation and Hydrogenation by C5Me4SiMe3-Ligated Di- and Trinuclear Chromium Hydride Complexes

Reduction of Dinitrogen to Ammonia at a Well-Protected Reaction Site in a Molybdenum Triamidoamine Complex

Synthesis of Ammonia through Direct Chemical Reactions between an Atmospheric Nitrogen Plasma Jet and a Liquid

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Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes

Dinitrogen Activation and Hydrogenation by C₅Me₄SiMe₃-Ligated Di- and Trinuclear Chromium Hydride Complexes