Catalytic composition

Abstract

The present invention relates to catalytic compositions which are particularly suitable for activating and breaking the N-N triple bonds of the elemental substance N2. The catalytic composition is capable of generating NH3 from elemental species N2 and H2. The catalytic composition comprises a vanadium compound, an organic proligand, and an alkali metal or alkaline earth metal base. The proligands are characterized by an organic molecular core and at least two arms, each arm containing an imidazole having two o-phenol substituents. A process for producing NH3 from elemental species N2 and H2 comprises the use of said catalytic composition and can be carried out at a temperature of less than 300 DEG C and a pressure of less than 200 bar. A forming gas containing N2 and H2 may be used as a reactant mixture. Production of organic nitrides from N2 and an olefin or from an olefin as a reducing substrate and decomposition of NH3 to regenerate H2 can also be achieved by using the catalytic composition.

Description

Technical Field

[0001] The present invention relates to a catalytic composition containing a vanadium compound, a proligand and a metal base. In addition, the present invention relates to the use of such a catalytic composition and the use of such a catalytic composition to activate N 2 For example, the element N 2 and H 2 Produces NH 3 method.

[0002] Since the Industrial Revolution, the world population has grown steadily. As a result of this development, food production must meet the growing demand, which has led to a greater demand for fertilizers, including nitrogen compounds. The most abundant nitrogen resource is gaseous nitrogen, which can be used to produce NH 3 Traditionally, the Haber-Bosch process uses an iron-based catalyst to produce NH at high temperatures and pressures. 3 Due to the high energy requirements of the HaberBosch process, alternative catalysts have been investigated. In view of the above, barium-promoted Ru-based catalysts have been provided (Non-Patent Literature (NPL) 1) and their NH 3 Such catalysts exhibit enhanced catalytic activity compared to conventional iron-based catalysts.

[0003] In addition, other metals including vanadium are also promising for N 2 Activation. Since vanadium can exist in multiple oxidation states, V-based catalysts are promising candidates. Therefore, catalysts for NH 3 However, the use of known V-based catalysts for the production of NH 3 It is necessary to add a strong reducing agent, potassium graphite (KC 8 ) and an excess of a strong Brookhart acid as a proton donor.

[0004] Non-patent document 1: Bielawa, H. et al. Angew. Chem. Int. Ed. 2001, Vol. 40, pp. 1061-1063.

[0005] Non-patent document 2: Sekiguchi, Y. et al. Angew. Chem. Int. Ed. 2018, Vol. 57, pp. 9064-9068.

[0006] However, the production of NH according to NPL 1 and NPL 2 3The methods of NPL 1 have several disadvantages. The application of Ru-based catalysts as disclosed in NPL 1 still requires unusually high temperatures of around 300°C, which is associated with high energy costs. The V-based catalysts of NPL 2 can be used at low temperatures, but require expensive and aggressive reducing agents and a high excess of acid for activation.

[0007] Therefore, the object of the present invention is to provide a 2 Activation and N 2 In addition, the elemental substance N should be provided. 2 and H 2 Generate NH 3 The method is carried out at low temperature and low pressure and does not require expensive reducing agents or proton donors.

[0008] The present inventors have conducted extensive quantum chemistry, organic synthesis, inorganic synthesis and catalysis research to provide solutions to the above problems and have found that a catalytic composition comprising a thermally stable proligand having a 4,5-bis(o-hydroxyphenyl)imidazole side arm, a vanadium compound and a metal base can be used to synthesize N 2 and H 2 Production of NH 3 . Catalysis of energy balance 2 The inventive nature of the activation mechanism is reversible and facile NN bond cleavage. The polarizing effect of the alkali or alkaline earth metal coordinated on the two nitrogen atoms provides a kinetically low barrier to the thermodynamic near equilibrium of the divanadium(IV) hydrazide on one side and the two vanadium(V) nitrides on the other side. The vanadium center must be sterically shielded by bulky substituents on the ligands to prevent aggregation by bridging μ-nitride or μ-imidate or μ-oxide ligands, thereby preventing deactivation of the obligatory coordinated active vanadium center.

[0009] Specifically, the object of the present invention is achieved by a catalytic composition comprising

[0010] Vanadium compounds, preferably molecular vanadium oxide halide complexes such as VOCl 2 (Dioxane) 2 or VOCl 2 (N-Morpholine) 2 ,

[0011] a proligand represented by the following formulae (1) to (23), and

[0012] Metal base:

[0013] Formula (1):

[0014]

[0015] Formula (2):

[0016]

[0017] Formula (3):

[0018]

[0019] Formula (4):

[0020]

[0021] Formula (5):

[0022]

[0023] Formula (6):

[0024]

[0025] Formula (7):

[0026]

[0027] Formula (8):

[0028]

[0029] Formula (9):

[0030]

[0031] Formula (10):

[0032]

[0033] Formula (11):

[0034]

[0035] Formula (12):

[0036]

[0037] Formula (13):

[0038]

[0039] Formula (14):

[0040]

[0041] Formula (15):

[0042]

[0043] Formula (16):

[0044]

[0045] Formula (17):

[0046]

[0047] Formula (18):

[0048]

[0049] Formula (19):

[0050]

[0051] Formula (20):

[0052]

[0053] Formula (21):

[0054]

[0055] Formula (22):

[0056]

[0057] Formula (23):

[0058]

[0059] Where E is a carbon atom, a silicon atom or a germanium atom, and Ar is a 2-substituted group R 1 and 4-substituent R 2 An o-hydroxyphenyl substituent, wherein R 1 is a branched or unbranched alkyl, aryl, alkylated / arylated silyl, or heteroaryl; and R 2 is H, branched or unbranched alkyl, aryl, alkylated / arylated silyl, heteroaryl; and R 3 is hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; and wherein the linking group is a divalent molecular organic fragment.

[0060] Further embodiments are characterized by the dependent claims.

[0061] The present invention provides a catalytic composition using a vanadium complex, an organic proligand and a metal base, which is suitable for a variety of catalytic redox reactions such as molecular N 2 The combination of components allows the activation of the catalyst by N under mild conditions of pressure below 200 bar and temperature below 300°C. 2 and H 2 Generate NH 3 , to reduce NH 3Energy costs for generation. In addition, no expensive or aggressive reducing agents and proton donors are required.

[0062] Hereinafter, embodiments of the present invention are described in detail.

[0063] According to the present invention, there is provided a catalytic composition comprising at least a proligand, a vanadium compound and a base, which are described in detail below.

[0064] Vanadium compounds

[0065] According to the present invention, a vanadium-containing compound is used in a catalytic composition to provide an active species having catalytic activity.

[0066] Vanadium constitutes an optimal catalytic center for redox reactions because vanadium can easily change its oxidation state. The most common oxidation states are +V and +IV, but +III and +II are also easily obtained, although they are more active. In addition, vanadium has a greater electropositivity than other metals, making it suitable for catalytic activity and ligand binding. Even further, in its low oxidation state, i.e., +III, vanadium is able to donate electrons to the ligand through π-backbonding, making the ligand's bond weaker, which is useful for non-reactive ligands such as molecular N 2 ) activation is particularly important.

[0067] However, when using vanadium, care must be taken due to the oxophilicity of vanadium. Since vanadium readily changes its oxidation state, oxidation states below +V are easily oxidized in air. Therefore, many of the preparation steps of the present invention are carried out in a dry and inert atmosphere.

[0068] In order to prepare the catalytic composition, vanadium compounds with various oxidation states can be used. Typically, vanadium in the oxidation states of +III, +IV and +V is used. However, in the redox reaction of the catalytic composition, the oxidation state of the vanadium is not fixed. When vanadium in the oxidation state of +IV or +V is selected, oxyvanadium compounds containing oxygen ligands can be used. Due to the high oxygen affinity of vanadium, the vanadium-oxygen bond is stable, and the oxygen ligand is most likely to be retained in the active catalyst formed by the catalytic composition.

[0069] In addition to the metal, the ligands of the vanadium compound have an important influence on the preparation of the catalytic composition. In particular, the coordination number of the vanadium is important for enabling the vanadium to easily bind to the pro-ligand described later. A low coordination number promotes binding to the pro-ligand, while a high coordination number hinders binding. Vanadium with few coordinating ligands tends to bind nucleophilic solvent molecules to achieve the preferred coordination number of 6 for vanadium. Therefore, since a portion of the ligand is easily dissociated, the ligand must be selected to achieve high reactivity of the vanadium compound.

[0070] In view of the above, polar solvents such as tetrahydrofuran (THF), dioxane or morpholine can be used to coordinate vanadium compounds. However, it is important that the solvent binds weakly and readily dissociates from the vanadium as a sacrificial ligand, thereby being able to bind to the proligand.

[0071] Furthermore, the vanadium compounds may contain one or more vanadium centres. While mononuclear vanadium compounds are readily available, binuclear vanadium compounds show increased reactivity before binding to ligands because in binuclear vanadium compounds the vanadium atoms are easily accessible, i.e., they are less spatially shielded by ligands than in mononuclear compounds.

[0072] Examples of vanadium compounds according to the invention are vanadium compounds having an oxidation number of +III, +IV or +V.

[0073] As an example of a vanadium compound with an oxidation number of +III, mention may be made of VCl 3 (thf) 3 、VCl(thf)(N(SiMe 3 ) 2 ) 2 、V(N(SiMe 3 ) 2 ) 3 、V(Mes) 3 (thf) and the compounds represented by formula (8-1) to (8-4), preferably VCl 3 (thf) 3 , as it can readily release chloride and tetrahydrofuran (THF) ligands to bind to the proligand.

[0074]

[0075] As an example of a vanadium compound having an oxidation number of +IV, mention may be made of VO(acac) 2 VOCl 2 (Dioxane) 2 VOCl 2 (N-Morpholine) 2 and compounds represented by formula (8-5) and (8-6), preferably VOCl 2 (Dioxane) 2 , as it can readily release chloride and dioxane ligands to bind to the proligand.

[0076]

[0077] As an example of a vanadium compound with an oxidation number of +V, VOCl can be mentioned. 2 (acac).

[0078] From the viewpoint of the availability of the vanadium compound and the proligand and the promotion of binding, VCl is most preferably used. 3 (thf) 3 or VOCl 2 (Dioxane) 2 .

[0079] Typical methods for providing the vanadium compound according to the present invention include metathesis reaction of lithium salts or Grignard compounds containing organic residues or amine residues with salts of vanadium halides in various oxidation states, or even vanadium compounds with low coordination numbers (e.g., VCl 3 ) is dissolved in a boiling polar solvent (such as THF or dioxane). The VOCl is described in detail in the following examples. 2 (Dioxane) 2 Exemplary preparation of.

[0080] Preligand

[0081] According to the present invention, the catalytic composition comprises a proligand. The proligand provides an environment for the active vanadium species in the catalytic reaction cycle. Therefore, the proligand needs to meet the steric and electronic requirements to achieve catalysis. Generally, in the catalytic redox cycle, the oxidation state of vanadium is +II to +V. Therefore, depending on the redox reaction to be catalyzed, it may be necessary to provide more than one vanadium center in the active catalyst to donate or accept the appropriate number of electrons. For example, N 2 Produces two NH 3 , requires three H 2 However, in the intermediates of the catalytic cycle, the electrons may be donated by vanadium atoms, which can facilitate catalysis if the proligand can bind more than one vanadium.

[0082] In view of the above, the function of the proligand is to provide a structure to bind more than one vanadium atom and to enable electron transfer between the different bound vanadium atoms.

[0083] In order to achieve the above functions, the proligands are represented by the following formulae (1) to (23).

[0084] Formula (1):

[0085]

[0086] Formula (2):

[0087]

[0088] Formula (3):

[0089]

[0090] Formula (4):

[0091]

[0092] Formula (5):

[0093]

[0094] Formula (6):

[0095]

[0096] Formula (7):

[0097]

[0098] Formula (8):

[0099]

[0100] Formula (9):

[0101]

[0102] Formula (10):

[0103]

[0104] Formula (11):

[0105]

[0106] Formula (12):

[0107]

[0108] Formula (13):

[0109]

[0110] Formula (14):

[0111]

[0112] Formula (15):

[0113]

[0114] Formula (16):

[0115]

[0116] Formula (17):

[0117]

[0118] Formula (18):

[0119]

[0120] Formula (19):

[0121]

[0122] Formula (20):

[0123]

[0124] Formula (21):

[0125]

[0126] Formula (22):

[0127]

[0128] Formula (23):

[0129]

[0130] wherein E is a carbon atom, a silicon atom, or a germanium atom, and Ar is a 2-substituted group R 1 and 4-substituent R 2 An o-hydroxyphenyl substituent, wherein R 1 is a branched or unbranched alkyl, aryl, alkylated / arylated silyl, or heteroaryl; and R 2 is H, branched or unbranched alkyl, aryl, alkylated / arylated silyl, heteroaryl; and R 3 is hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; and wherein the linking group is a divalent molecular organic fragment.

[0131] In formulae (1) to (23), the core of the proligand is composed in particular of benzene, biphenyl, adamantane, triphenylamine, 1,3,5-triphenylbenzene, tetraphenylsilane or a linked bis(triphenylsilyl) structure. Two to twelve imidazole residues are bound to the core (these imidazole residues are referred to as "arms" hereinafter) and also contain phenol substituents. Thus, the basic structure of formulae (1) to (23) provides a rigid conjugated structure that is able to transport electrons due to its aromatic properties. In addition, the described structure is exceptionally thermally stable, which allows long-term application at temperatures exceeding 200° C. The rigid structure of the proligand provides a basis for a stable coordination center for binding vanadium, which may be unstable in a less rigid system due to the aggregation of different parts.

[0132] In addition, it is apparent from formulas (1) to (23) that the pro-ligand contains multiple metal binding sites. In particular, each imidazole arm contains four nucleophilic binding sites, which are two nitrogen atoms in the imidazole ring and two oxygen atoms of the phenol substituent. Therefore, each bound vanadium atom is surrounded by a chelating ligand system of one oxygen atom and one nitrogen atom, which provides the basis for stabilizing the catalyst. Due to the chelation of the two nucleophilic atoms, the strong binding of vanadium increases the thermal stability of the active catalyst. In contrast, pro-ligands that do not contain imidazole arms are not so thermally stable and cannot be used in typical catalytic applications.

[0133] The phenol rings in formulae (1) to (23) may contain additional residues R 1 , R 2 and R 3 . These residues may have an effect on solubility and crystallization tendency, thereby affecting the preparation of the pro-ligand. Specifically, an increased crystallization tendency leads to an increased yield of the pro-ligand and simplified purification. In addition, these residues can provide steric shielding of the vanadium binding site, which reduces the aggregation of active catalysts, resulting in reduced deactivation. Preferably, these residues are branched alkyl groups because of the steric shielding effect of branched alkyl groups and the increased crystallization tendency. More preferably, the residues are tert-butyl or tert-amyl, which are advantageous for the increased crystallization tendency and shielding of the vanadium binding site, while maintaining suitable gas diffusion during the catalytic process.

[0134] Typical residues R 1 and R 2 The alkyl group of the present invention is H, a branched alkyl group or an unbranched alkyl group. Examples of branched alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl and branched pentyl groups. Examples of unbranched alkyl groups include methyl, ethyl, n-propyl, n-butyl and n-pentyl. Small and symmetrical alkyl groups such as tert-butyl and tert-pentyl groups that increase the crystallization tendency of the proligand are preferred. In view of the solubility in non-polar solvents during the preparation process, the length of the alkyl group can be optimized according to the solvent used. In addition, branched alkyl groups with high spatial requirements, such as isopropyl and tert-butyl, are preferred because they have a shielding effect on the proligand.

[0135] The proligand contains two or more imidazole arms, each of which contains two chelated vanadium binding sites, so the proligand includes at least two regions capable of binding to two vanadium atoms opposite to each other. These binding regions are referred to as "binding pockets" hereinafter. Since the binding pocket is located between the imidazole arms, each proligand contains more than one binding pocket, usually 2 to 8 binding pockets. The size of the binding pocket depends mainly on the core of the proligand and the position of the imidazole arms at the core. For example, the proligand with three imidazole arms represented by formula (1) contains three binding pockets. The four binding pockets in formula (2) have different sizes, depending on whether the imidazole arms are in the meta position of the same phenyl group in the biphenyl core or across two phenyl groups. The proligand represented by formula (2) contains four binding pockets, two of which are small (i.e., binding pockets surrounded by imidazole arms bound to the meta position of the same phenyl ring of the core), and two are large (i.e., binding pockets surrounded by imidazole arms bound to different phenyl rings of the core). In formula (3), there are four large pockets. In formula (4) and (5), there are three small binding pockets and three large binding pockets, respectively. In formula (6), there are four small binding pockets and four large binding pockets. In formula (7), there are six small binding pockets and at most six large binding pockets. Eight vanadium atoms are present in the complexes of the proligands of formula (8), (9), (10), (11), (13), (14) and (20). Twelve vanadium atoms are present in the complexes of the proligands of formula (12), (17), (18) and (23). Four vanadium atoms are present in the complexes of the proligands of formula (15) and (16). Sixteen vanadium atoms are present in the complex of the proligand of formula (19) with n=8. At least one binding pocket in the catalytic complex must avoid aggregation / deactivation of its two vanadium centers, respectively.

[0136] In view of the above, the position and number of the imidazole arms of the proligand constitute important parameters for tuning the catalytic composition of the catalytic substrate.

[0137] According to the present invention, the proligand represented by formula (1) having an imidazole arm at the meta position and the proligand represented by formulas (2) to (23) are effective for binding two vanadium atoms in each binding pocket and enabling the vanadium atom to bind to the N bridge between the two vanadium centers. 2 The ligand is optimal. Two vanadium atoms and one N 2 Ligand binding leads to easier N 2 activation, which is due to N 2 Stronger binding and N 2 Even more preferred is a more distal position of the imidazole arm as represented by formula (2). The described catalytic composition is used for the removal of N 2 Catalytic reactions other than activation (eg, reactions of alkynes and alkenes) may make large binding pockets such as those in (2) to (23) more suitable.

[0138] In the following, an exemplary synthetic route for preparing a proligand is described. However, the present invention is not limited to this specific synthetic route. In addition, an exemplary synthetic route for a specific proligand is described in more detail in the examples.

[0139] Starting from 2-halogen substituted anisole derivatives, elemental lithium can be used to generate C-nucleophilic lithium anisole derivatives, which can then react with gaseous CO. The dilithium endiolate product can be chemically activated with MnO 2 Oxidation. This reaction produces a dimeric anisole derivative which is then deprotected to produce a dimeric phenol derivative, hereinafter referred to as 1,2-diketone. The synthesis of this intermediate component is shown in Scheme 1 below.

[0140] Scenario 1:

[0141]

[0142] Where R 1 can be selected from alkyl, aryl, silyl and heteroaryl, R 2 can be selected from hydrogen, alkyl, aryl, silyl and heteroaryl, R 3 represents a moiety having at least two imidazole-derived substituents ("linking group"), and X represents a halogen substituent such as Cl, Br or I, preferably Br.

[0143] Subsequently, the diketone is added to the aromatic aldehyde (forming the core of the proligand) and ammonium acetate in acetic acid. Thus, in a modified Debus-Radziszewski imidazole synthesis, the imidazole ring is formed to produce the final proligand. The methyl protecting group can be provided, for example, by adding a CH 2 Cl 2 BBr 3 Remove.

[0144] In the next chapter on the preparation of proligands, the synthetic schemes of three examples (compounds 4, 5 and 7) are provided, thus demonstrating the proposed modular principle with different core and peripheral modules.

[0145] Metal base

[0146] According to the present invention, the catalytic composition comprises a base. The base is included to deprotonate the proligand, to bind the additional halide ligand of the vanadium compound, and to activate the bound N 2 molecular.

[0147] In particular, the base must be able to deprotonate the phenolic hydroxyl group and the acidic protons of the imidazole ring. The deprotonation of said groups provides the basis for the strong coordination of vanadium with the pre-ligand. Strong coordination is necessary for the application of the catalytic composition at high temperatures.

[0148] Preferably, the base contains a metal. In particular, the metal is selected from Li, Na, K, Mg, and Ca. Using a metal-containing base enables the base to react with the halide ligand of the vanadium compound. Due to the metathesis reaction of the metal-containing base with the salt of the vanadium compound having a halide ligand, the ligand is removed in the case of forming a stable metal halide salt. In addition, the introduction of the metal contributes to the activation of N 2 which can serve as a substrate for the catalysis to be carried out. In particular, metal ions can polarize the N 2 bonded to the catalytic complex and further destabilize the N-N bond, resulting in increased activation of the substrate. In view of the above, the preferred metals are Li, Na, and K, and most preferably lithium.

[0149] Regarding the deprotonation efficiency, a strong base should be used for the deprotonation of the pre-ligand. The preferred base is a metal hydride or a metal salt of a branched or unbranched alkyl compound or an aryl compound. More preferably, the base is potassium hydride, sodium hydride, or a lithium salt of a branched or unbranched alkyl compound. Even more preferably, the base is potassium hydride or n-butyllithium. Most preferably, the base is n-butyllithium.

[0150] According to the present invention, one base can be used alone, or more than one base can be used in combination.

[0151] Catalytic composition

[0152] Hereinafter, the amounts of the components of the catalytic composition are described in terms of their amounts relative to one equivalent of the pre-ligand.

[0153] Generally, the vanadium compound is included according to the number of imidazole arms of the pre-ligand. Each imidazole arm can bind two vanadium atoms. Thus, for one equivalent of the imidazole side arm in the pre-ligand, the catalytic composition contains at least two equivalents of the vanadium compound. This means, for example, adding four equivalents of the vanadium compound (e.g., VOCl 2 (dioxane) 2 ) to the pre-ligand having two imidazole arms, adding six equivalents of the vanadium compound to the pre-ligand having three imidazole arms, and adding eight equivalents of the vanadium compound to the pre-ligand having four imidazole arms. To improve the binding of vanadium atoms to the pre-ligand, an excess of the vanadium compound can be added.

[0154] Depending on the number of acidic protons in the proligand, or the number of vanadium equivalents, the number of halide ligands of the vanadium compound, and the substrate to be catalyzed, a metal base is included in the catalytic composition. Preferably, at least one equivalent of a metal base should be added for each vanadium and each halide in the vanadium compound.

[0155] For example, if the proligand represented by formula (2) is used, 12 acidic protons must be deprotonated, which requires 12 equivalents of a metal base such as BuLi. 2 (Dioxane) 2 The eight vanadium and 16 chlorine ligands of the catalyst require 24 BuLi, so after combining the fully lithiated ligands and the vanadium(IV) compound, an additional 12 BuLi have been added.

[0156] A slight excess of metal base leads to a higher content of active catalytic compounds, thus defining the ratio of vanadium (IV) to vanadium (V) and thus influencing the redox potential of the system. In other words, the amount of lithium, for example, is the adjusting screw for the activity of the catalytic system.

[0157] In addition, other components can be incorporated into the catalyst composition. Preferably, a support material can be used because it is conducive to increasing the reaction surface area of ​​the catalyst composition. The increase in surface area can produce more available catalytic centers and improved catalysis. Therefore, a variety of solid support materials with high surface area can be used. Preferably, diatomaceous earth, silica gel, graphite, soot (soot), aluminum oxide, aluminosilicate, vanadium oxide or titanium dioxide can be used as support material.

[0158] Use of the catalytic composition

[0159] Exemplary uses of the catalytic composition according to the invention include the activation of molecular nitrogen or the reaction of unsaturated hydrocarbons. Specific examples of the use of the catalytic composition are composed of elemental substances N 2 and H 2 Synthetic NH 3 , N 2 Reduction to N(SiMe 3 ) 3 , reactions of steam cracker gases (e.g. hydrogenation or olefin metathesis).

[0160] The proligand can be adjusted depending on the use of the catalytic composition. In particular, the size of the binding pocket for the vanadium and the catalyzed substrate can be optimized for each substrate.

[0161] From elemental substance N 2 and H 2 Generate NH 3 Methods

[0162] According to the present invention, the elemental substance N 2 and H 2 Generate NH3 The method can be carried out using the above-mentioned catalytic composition. The catalytically active vanadium complex is generated in situ from the catalytic composition.

[0163] By N 2 and H 2 Generate NH 3 The method can be compared with traditional NH 3 In particular, NH 3 The generation can be carried out at a temperature below 300° C. and a pressure below 200 bar. Carrying out under these conditions ensures the stability of the active catalyst produced by the catalytic composition according to the invention. In view of the cost, it is preferred to carry out the NH generation at a temperature below 200° C. and a pressure below 30 bar. 3 Further, NH 3 The synthesis has been successfully carried out under standard pressure.

[0164] As reactant mixture, any forming gas may be used, i.e., N 2 and H 2 Any mixture of N 2 :H 2 The ratio is 1:3 (this means that NH 3 The stoichiometric ratio of the two reactants in the formation of the forming gas is 2. 2 :H 2 A 95:5 ratio forming gas is less hazardous for laboratory experiments, where the remaining hydrogen can be vented into a laboratory exhaust hood.

[0165] In another embodiment, the present invention relates to basic vanadium complexes or alkaline earth metal vanadium complexes having at least two 4,5-bis(o-hydroxyphenyl)imidazole derived substituents at the central linker module, which catalyze the N-N bond reduction of coordinated vanadium(IV) or the oxidation of two nitrides of coordinated vanadium(V), or both. Typical coordination numbers of the vanadium atoms in these complexes are 4 and 5.

[0166]

[0167] M=Li, Na, K, MgX, CaX; preferably lithium

[0168] L=NH 2 NH 3 or free coordination site

[0169] [V] = vanadium ion with another oxide, alkoxide, phenolate, nitride, imide, amide or ammine ligand.

[0170] R 1= alkyl, aryl, silyl, heteroaryl

[0171] R 2 =H, alkyl, aryl, silyl, heteroaryl

[0172] Linking group = a molecular fragment containing a thermally stable CC, CN, CO, C-Si or CP bond and covalently links two or more imidazole groups as shown. General examples are alkylsilanes, arylsilanes, alkylarylsilanes, aryl ethers, arylamines, arylphosphines, arylphosphine oxides, alkanes and cycloalkanes, aromatic and heteroaromatic systems, cyclic aromatic and cyclic heteroaromatic systems. Specific examples are m-phenylene, 3,3'-biphenylene and 1,3 adamantyl. Example

[0173] Hereinafter, the present invention will be described in detail based on Examples. However, the present invention is not limited to the following Examples.

[0174] Materials and measurement methods

[0175] Material

[0176] All reagents and solvents were stored in a nitrogen-filled glove box before use. Anhydrous solvents were obtained from an MBraun MB SCS-800 solvent purification system containing appropriate desiccants. THF was distilled over sodium and then degassed before being stored over molecular sieves. Celite and graphite were dried at 350 °C under high vacuum for 1 day. Potassium hydride was washed with THF and hexane and dried under high vacuum. N used for the Schlenk line 2 / H 2 The gas mixture is continuously directed through a column of potassium hydride to remove oxygen and water impurities.

[0177] Nuclear Magnetic Resonance (NMR) Spectroscopy

[0178] Recorded at room temperature 1H-NMR spectra were obtained using the following spectrometers: Bruker Avance III 300 (300 MHz), Bruker Avance DRX 300 (300 MHz), Bruker Avance III 400 (400 MHz), Bruker Avance III 600 (600 MHz). Chemical shifts δ are expressed in ppm and are determined with reference to the residual 1H-solvent peak (acetone: 2.05 ppm; benzene: 7.16 ppm; chloroform: 7.26 ppm; deuterium oxide: 4.79 ppm; dichloromethane: 5.32 ppm; dimethyl sulfoxide (DMSO): 2.50 ppm; THF: 1.73 ppm, 3.58 ppm). Coupling constants J are in Hz. The following abbreviations describe the observed multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, m = multiplet (combined abbreviations refer to multiple coupling modes, the first letter indicating the larger coupling constant). 13 C{ 1 H} NMR spectra were recorded at room temperature using the following spectrometers: Bruker Avance III 400 (100 MHz), Bruker Avance III 600 (150 MHz). The spectra were calibrated relative to the solvents (acetone: 29.84 ppm, 206.26 ppm; benzene: 128.39 ppm; chloroform: 77.16 ppm; dichloromethane: 53.84 ppm; DMSO: 39.52 ppm). All observed signals were singlet. For the processing, analysis and interpretation of NMR spectra, the program TopSpin 3.5 from Bruker was used.

[0179] reaction

[0180] All reactions were performed under nitrogen or argon atmosphere using glove box and Schlenk line techniques.

[0181] NH 3 Generated Assessment

[0182] The catalytic composition was placed in a mild N 2 / H 2 The gas stream was directed through a column having known amounts of dimethyl sulfone (as an internal standard) and methanesulfonic acid (for acidification of the generated NH 3 , which is used to capture NH 3 ) 6 -DMSO solution. The NH 4 + pass 1The H-NMR spectrum was detected by its triplet signal between 6.9 and 7.4 ppm. Each production experiment was carried out at least twice. 3 The test results generated are shown in Table 1. If NH 3 , the corresponding embodiment is marked with "Y" (yes), if no NH 4+ , the corresponding embodiment is marked as "N" (No).

[0183] Preparation of proligand

[0184] Production Example 1

[0185]

[0186] A flask was charged with 20 ml of a THF solution of 2-bromo-4,6-di-tert-butylanisole (3.50 g, 11.7 mmol, 1.00 equivalent). Lithium particles (0.18 g, 25.7 mmol, 2.20 equivalent) were added and the mixture was stirred at 0 ° C for 1 h. The reaction mixture was transferred dropwise to a flask, the flask was rinsed with carbon monoxide (CO) and cooled to -115 ° C. The mixture was stirred at -115 ° C for 6 h under a CO atmosphere. Manganese dioxide (2.03 g, 23.3 mmol, 2.00 equivalent) was added and changed to an argon atmosphere. After the mixture was stirred at room temperature overnight, it was filtered with diatomaceous earth. The crude product was evaporated under reduced pressure and recrystallized from methanol. Compound 1 (3.45 g, 6.97 mmol, 60% yield) was isolated as a light yellow solid.

[0187]

[0188] 1 H NMR (300.51 MHz, CDCl 3 , 300.0K): δ=7.59(d, 4 J H-H =2.5Hz, 2H, H-4), 7.33(d, 4 J H-H =2.5Hz, 2H, H-11), 3.58 (s, 3H, H-9), 1.27 (s, 9H, H-7), 1.05 (s, 9H, H-1)ppm.

[0189] 13 C{ 1 H}NMR (75.56 MHz, CDCl 3, 300.0K): δ=195.9(C-12), 158.5(C-8), 146.0(C-3), 142.0(C-5), 130.4(C-4), 128.9 (C-11), 126.2(C-10), 65.4(C-9), 34.9(C-6), 34.6(C-2), 31.4(C-7), 30.6(C-1)ppm.

[0190] Production Example 2

[0191]

[0192] A 30ml dichloromethane (DCM) solution of compound 1 (3.40g, 6.87mmol, 1.00 equivalent) was loaded into a flask. The mixture was cooled to -78 °C and boron tribromide (9.32g, 37.2mmol, 3.00 equivalent) was added dropwise. Stirring was continued at room temperature for 1 day. The final mixture was poured on ice, washed with water and dried with magnesium sulfate. Tartaric acid (5.15g, 34.3mmol, 5.00 equivalent) was added to the mixture of the crude product in methanol, and the solution was refluxed for 2h. The reaction mixture was evaporated, redissolved in DCM, washed with water and dried with magnesium sulfate. Crude compound 2 was purified by silica gel column chromatography (PE) to obtain a yellow solid (2.50g, 5.36mmol, 82% yield).

[0193]

[0194] 1 H NMR (300.51 MHz, CDCl 3 , 300.0K): δ = 12.0 (s, 2H, H-9), 7.65 (d, 4 J H-H =2.3Hz, 2H, H-4), 7.27(d, 4 J H-H =2.3Hz, 2H, H-11), 1.47 (s, 18H, H-7), 1.22 (s, 18H, H-1)ppm.

[0195] 13 C{ 1 H}NMR (75.56 MHz, CDCl 3 , 300.0K): δ=197.7(C-12), 161.4(C-8), 141.3(C-3), 138.5(C-5), 133.4(C-4), 126.0(C-11), 115.9(C-10), 35.2(C-6), 34.2(C-2), 31.2(C-7), 29.4(C-1)ppm.

[0196] Production Example 3

[0197]

[0198] A flask was charged with a solution of compound 2 (7.90 g, 16.9 mmol, 4.10 equiv), compound 3 (1.10 g, 4.13 mmol, 1.00 equiv) and ammonium acetate (7.96 g, 0.10 mol, 25.0 equiv) in acetic acid (140 ml). The resulting mixture was stirred at 130 ° C for 7 days. After cooling to room temperature, the mixture was filtered and the residue was washed with acetic acid. The crude compound 4 was recrystallized from toluene to produce a colorless solid (6.20 g, 3.02 mmol, 73% yield).

[0199]

[0200] 1 H NMR (600.24 MHz, CD 2 Cl 2 , 300.0K): δ = 12.55 (s, 4H, H-13), 9.86 (s, 4H, H-12), 8.61 (s, 2H, H-9), 8.19 (d, 4 J H-H =1.5Hz, 4H, H-10), 7.50(d, 4 J H-H =2.5Hz, 4H, H-6 / 7), 7.30(d, 4 J H-H =2.5Hz, 4H, H-6 / 7), 7.17(d, 4 J H-H =2.5Hz, 4H, H-5 / 8), 7.10(d, 4 J H-H =2.5Hz, 4H, H-5 / 8), 5.30 (s, 4H, H-11), 1.44 (s, 36H, H-1 / 4), 1.42 (s, 36H, H-1 / 4), 1.32 (s, 36H, H-2 / 3), 0.97 (s, 36H, H-2 / 3)ppm.

[0201] 13 C{ 1 H}NMR (150.93 MHz, CD 2 Cl 2, 300.0K): δ = 153.2 (C-28), 150.4 (C-29), 143.3 (C-21 / 25), 142.2 (C-21 / 25), 140.3 (C-19 / 23), 140.0 (C-19 / 23), 138.0 (C-18 / 22), 136.4 (C-18 / 22), 130.4 (C-26 and 27), 129.0 (C-toluene), 128.2 (C-toluene), 126.1 (C-5 / 8), 125.4 (C-5 / 8), 125.2 (C-9), 124.6 (C-toluene), 123.6 (C-6 / 7), 121.8 (C-10), 121.7 (C-30), 120.5 (C-6 / 7), 117.4 (C-20 / 24), 115.5 (C-20 / 24), 35.1 (C-14 and 17), 34.6 (C-15 / 16), 33.9 (C-15 / 16), 32.2 (C-2 / 3), 31.1 (C-2 / 3), 29.5 (C-1&4) ppm.

[0202] 1,3,5-Tris[4,5-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1H-imidazol-2-yl]benzene

[0203]

[0204] Under an argon atmosphere, a flask was charged with a solution of 1,2-bis(3,5-di-tert-butyl-2-hydroxyphenyl)ethanedione compound 2 (1.81 g, 3.89 mmol, 3.10 equivalents), benzene-1,3,5-tricarbaldehyde (0.18 g, 1.11 mmol, 1.00 equivalents) and ammonium acetate (1.71 g, 22.20 mmol, 20.00 equivalents) in acetic acid (36 ml). The resulting mixture was stirred at 130° C. for 10 days. After cooling to room temperature, the mixture was filtered, and the residue (compound 5·3AcOH) was washed with acetic acid and diethyl ether (1-3 ml) to obtain a colorless solid compound 5 (1.63 g, 0.95 mmol, 85%).

[0205]

[0206] 1 H NMR (600.24 MHz, CDCl 3, 300.0K): δ = 13.01 (s, 3H, H-28), 10.53 (s, 3H, H-9), 8.56 (s, 3H, H-27), 7 .58(s, 3H, H-11 / 15), 7.38(s, 3H, H-11 / 15), 7.27(s, 3H, H-4 / 19), 7.27(s, 3H, H-4 / 19), 7.21 (s, 3H, H-4 / 19), 5.32 (s, 3H, H-24), 1.54 (s, 27H, H-22 / 7 ), 1.53 (s, 27H, H-22 / 7), 1.42 (s, 27H, H-1 / 18), 1.07 (s, 27H, H-1 / 18) ppm.

[0207] 13 C{ 1 H}NMR (150.93 MHz, CDCl 3 , 300.0K): δ=153.2(C-25), 150.4(C-26), 143.4(C-8 / 23), 142.8(C-8 / 23), 140.6(C -3 / 16), 139.8(C-3 / 16), 136.6(C-5 / 20), 136.5(C-5 / 20), 130.4(C-12 / 13), 126.2(C 12 / 13), 125.3(C-4 / 19), 123.9(C-4 / 19), 122.3(C-11 / 15), 121.8(C-27), 120.4(C 11 / 15), 117.4(C 10 / 14), 115.5(C-10 / 14), 35.3(C--6-21), 34.6(C-2 / 17), 34.0(C-2 / 17), 31.7(C-1 / 18), 31.3(C-1 / 18), 29.9(C-7-22)ppm.

[0208] Elemental analysis (No. 41747)

[0209] [M+AcOH] calcd: C: 77.65, H: 8.78, N: 5.38

[0210] Found: C: 77.83, H: 8.83, N: 5.54 HR-MS (ESI + , DCM / MeOH) m / z (%):

[0211] [MH] Calculated: 1503.0315

[0212] Measured value: 1503.0333

[0213] IR(ATR)v=3522(m), 2954(s), 2869(m), 1607(w), 1439(s), 1361(s), 1198(m), 835(m)cm -1 .

[0214] Melting point: 253℃

[0215] Compound 5·3AcOH (600.24MHz, CDCl 3 , 300.0K) 1 H NMR: δ=8.75(s, 3H, H-14), 7.37(d, 3 J H-H =2.3Hz, 6H, H-10), 7.27(d, 3 J H-H =2.3Hz, 6H, H-4), 1.89 (s, 12H, H-15), 1.48 (s, 54H, H-10), 1.21 (s, 54H, H-1)ppm.

[0216] Compound 5·3AcOH (150.93MHz, CDCl 3 , 300.0K) 13 C{ 1 H}NMR: δ=176.9(C-16), 151.4(C-12), 143.6(C-8), 142.1(C-3), 136.5(C-5), 131.2(C-13), 130.4(C-9), 129.9( C-11), 124.8(C-13), 122.2(C-4), 117.0(C-14), 35.3(C-6), 34.3(C-2), 31.5(C-7), 29.9(C-1), 20.4(C-15)ppm.

[0217]

[0218] 1,3,5-Tris[4,5-bis(3,5-di-tert-pentyl-2-hydroxyphenyl)-1H-imidazol-2-yl]benzene

[0219]

[0220] Diketone compound 6 (1.00 g, 1.91 mmol, 3.5 equivalents) was dissolved in acetic acid (20 ml) under an argon atmosphere. Ammonium acetate (1.05 g, 13.7 mmol, 25 equivalents) and benzene-1,3,5-tricarbaldehyde (88.6 mg, 0.55 mmol, 1 equivalent) were added. The reaction mixture was heated to 130 ° C and stirred for 4 days. After cooling to room temperature, the reaction mixture was poured into water and extracted with ether (3×30 ml). The organic layer was neutralized twice with saturated sodium bicarbonate solution (20 ml) and washed three times with water (20 ml). After drying with magnesium sulfate and recrystallization from hot methanol, triimidazole compound 7 (716 mg, 0.429 mmol, 78%) was obtained in the form of a light yellow solid.

[0221]

[0222] 1 H NMR (300.51 MHz, CDCl 3 , 300.0K): δ = 13.13 (s, 3H, H-12), 10.85 (s, 3H, NH), 8.55 (s, 3H, H-1), 7.38 ( s, 3H, H-7), 7.24 (s, 3H, H-9), 7.11 (s, 3H, H-16), 7.08 (s, 3H, H-14), 5.24 (s 3 J H-H =5.4Hz, 18H, 23+33), 1.96(q, 3 J H-H =5.7Hz, 12H, H-22+32), 1.67(q, 3 J H-H =5.4Hz, 6H, H-27), 1.41(s, 36H, H-25+26+35+36), 1.36(q, 3 J H-H =5.4Hz, 6H, H-37), 1.31 (s, 18H, H-24+31), 0.95 (s, 18H, H-21+30), 0.75 (t, 3 J H-H =5.4Hz, 18H, 23+33), 0.69(t, 3 J H-H =5.7Hz, 9H, H-38), 0.54(t, 3 J H-H =5.4Hz,9H,H-28)ppm.

[0223] 13 C{ 1 H}NMR (125.76 MHz, CDCl 3, 300.0K): δ=153.1(C-11), 150.4(C-18), 143.0(C-17), 141.3(C-3), 140.0(C-15), 139.9(C-5), 134.8(C-10), 13 4.7(C-8), 130.3(C-2), 128.1(C-7), 126.1(C-9), 125.9(C-14), 122.2(C-4), 121.8(C-1), 121.2(C-16), 117.6(C -13), 115.5(C-6), 38.9(C-20), 38.9(C-43), 37.8(C-27), 37.2(C-39), 37.1(C-37), 36.9(C-27), 33.4(C-22), 33 .2(C-32), 28.9(C-25+35), 28.2(21+30), 27.9(26+36), 27.8(24+31), 9.7(C-23+33), 9.4(C-38), 9.2(C-28)ppm.

[0224] IR(ATR)ν=3520(w), 3238(w), 2962(s), 2875(w), 1709(w), 1559(s), 1476(s), 1361(m), 1329(w), 1297(w), 1248(m), 1168(w), 1168(w), 1106(w), 1080(w), 880(w), 854(w), 783(w), 701(m), 665(w), 648(w), 617(w)cm -1 .

[0225] VOCl 2 (Dioxane) 2 Preparation

[0226] Production Example 4

[0227]

[0228] Place 75 ml of vanadium trichloride (VCl 3 ) (1.82 g, 11.5 mmol, 3.00 equiv) in anhydrous dioxane. The suspension was heated to 90°C and stirred for 1 hour. Then vanadium pentoxide (V pentoxide) was added. 2 O 5 ) (0.70 g, 3.85 mmol, 1.00 equiv) and the mixture was stirred again at 90°C for 1 hour. Vanadyl chloride (VOCl) was then added rapidly 3) (0.76 g, 0.36 ml, 3.85 mmol, 1.00 equiv), the resulting dark red mixture was refluxed overnight. The resulting blue suspension was filtered and washed with dioxane to obtain a dark blue solution. After standing overnight, a blue precipitate was formed. The suspension was filtered again, and the crude product was recrystallized twice from dioxane to obtain VOCl in the form of a blue solid 2 (Dioxane) 2 (5.45 g, 17.3 mmol, 75%).

[0229] Preparation of catalytic composition

[0230] Example 1

[0231] The flask was charged with a solution of compound 4 (0.20 g, 97.42 μmol, 1.00 eq) in 20 ml of anhydrous THF. The solution was cooled to -78 °C and n-butyl lithium (0.76 ml, 1.60 M, 1.22 mmol, 12.5 eq) was added dropwise as a base, resulting in a strong yellow color, and stirring was continued for 1 h. Afterwards, 20 ml of the vanadium compound VOCl was added dropwise at -116 °C. 2 (Dioxane) 2 (0.25 mg, 0.79 mmol, 8.20 equiv) in anhydrous THF, causing the color to quickly turn dark black. The resulting mixture was stirred at room temperature for 1 day. To generate excess lithium, the solution was cooled to -116 ° C and n-BuLi (0.36 ml, 1.6 M, 0.58 mmol, 6.00 equiv) was added dropwise.

[0232] Example 2

[0233] A catalytic composition was obtained in the same manner as in Example 1, except that in the subsequent NH 3 The composition of the forming gas was changed during the generation experiment.

[0234] Example 3

[0235] A catalytic composition was obtained in the same manner as in Example 1, except that diatomaceous earth was added as a support material for the catalytic composition in the final step.

[0236] Example 4

[0237] A catalytic composition was obtained in the same manner as in Example 1, except that graphite was added as a support material for the catalytic composition in the final step.

[0238] Examples 5 to 8

[0239] The catalytic compositions were obtained in the same manner as in Examples 1 to 4, except that an increased amount of the base n-BuLi (0.54 ml, 1.6 M, 0.87 mmol, 9.00 equivalents) was added to generate an excess of lithium in the final step of preparing the catalytic composition.

[0240] Comparative Example 1

[0241] A composition was obtained in the same manner as in Example 1, except that the pre-ligand was omitted.

[0242] Comparative Example 2

[0243] A composition was obtained in the same manner as in Example 1, except that the vanadium compound was omitted.

[0244] Comparative Example 3

[0245] A composition was obtained in the same manner as in Example 1, except that in the subsequent NH 3 generation experiment, the gas composition did not contain H 2 .

[0246] NH 3 Generation

[0247] Then, the resulting suspensions of Examples 1 - 8 and Comparative Examples 1 - 3 were dried under high vacuum, and the residue was taken back into the glove box for transfer to a U-shaped glassware. The glassware was connected to a Schlenk line and placed under a gentle N 2 / H 2 gas stream at standard pressure while being heated to 200 °C. After passing through the catalytic composition, the gas stream was directed through a d 6 -DMSO solution having a known amount of dimethyl sulfoxide (as an internal standard) and methanesulfonic acid (for acidifying the generated ammonia, i.e., for capturing ammonia). For each example and comparative example, at least 2 experiments were conducted to test the reproducibility of NH 3 generation.

[0248] Table 1

[0249] Example Preligand V Compound <![CDATA[Base equivalent 1 > Carrier <![CDATA[N 2 :H 2 ]]> <![CDATA[NH 3 Generate]]> Example 1 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 - 1:3 Y Example 2 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 - 95:5 Y Example 3 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 diatomite 1:3 Y Example 4 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 graphite 1:3 Y Example 5 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 21.5 - 1:3 Y Example 6 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 21.5 - 95:5 Y Example 7 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 21.5 diatomite 1:3 Y Example 8 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 21.5 graphite 1:3 Y Comparative Example 1 - <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 - 1:3 N Comparative Example 2 Compound 4 - 18.5 - 1:3 N Comparative Example 3 Compound 4 <![CDATA[VOCl 2 (Dioxane) 2 ]]> 18.5 - 1:0 N

[0250] 1 Equivalents of base relative to 1.00 equivalent of pre-ligand

[0251] As can be seen from Table 1, NH 3 generation has been achieved with the catalytic compositions of Examples 1 to 8. Reproducible NH 3However, the comparative example 1 lacking the proligand, the comparative example 2 lacking the vanadium compound and the comparative example using N 2 Comparative Example 3, in which the gas was substituted for the molding gas, did not show NH 3 generate.

Claims

1. A catalytic composition comprising Vanadium compounds, preferably molecular vanadium oxide halide complexes, Preligand, Features an imidazole fragment having two ortho-phenol substituents, the substituents being represented by any one of the following: formula (1) or (2) or (3) or (4) or (5) or (6) or (7) or (8) or (9) or (10) or (11) or (12) or (13) or (14) or (15) or (16) or (17) or (18) or (19) or (20) or (21) or (22) or (23), and A base having an alkali metal or an alkaline earth metal, Formula (1): Formula (2): Formula (3): Formula (4): Formula (5): Formula (6): Formula (7): Formula (8): Formula (9): Formula (10): Formula (11): Formula (12): Formula (13): Formula (14): Formula (15): Formula (16): Formula (17): Formula (18): Formula (19): Formula (20): Formula (21): Formula (22): Formula (23): wherein E is a carbon atom, a silicon atom, or a germanium atom, and Ar is a 2-substituted group R 1 and 4-substituent R 2 An o-hydroxyphenyl substituent, wherein R 1 is a branched or unbranched alkyl, aryl, alkylated / arylated silyl, or heteroaryl; and R 2 is H, branched or unbranched alkyl, aryl, alkylated / arylated silyl, heteroaryl; and R 3 is hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; and wherein the linking group is a divalent molecular organic fragment.

2. The catalytic composition according to claim 1, wherein the base is a base containing a metal selected from the group consisting of lithium, sodium, potassium, magnesium and calcium.

3. The catalytic composition according to claim 1 or 2, wherein the base is a metal hydride such as potassium hydride, or a metal salt of a branched or unbranched alkyl compound or an aryl compound such as butyllithium or methyllithium or phenyllithium.

4. The catalytic composition according to any one of claims 1 to 3, wherein a large active surface of the catalyst composition is achieved using a support material such as graphite, soot, diatomaceous earth, silica gel, alumina, aluminosilicates, vanadium oxides or titanium dioxide.

5. The catalytic composition according to any one of claims 1 to 4, comprising two or more equivalents of the vanadium precursor compound per imidazole substituent and at least one equivalent of the metal base per vanadium and per halide equivalent in the vanadium precursor complex.

6. The catalytic composition according to any one of claims 1 to 5 is used for N 2 Activation of N 2 The reaction of H 2 Activation of H 2 or the reaction of alkynes and alkenes.

7. A catalytic composition according to any one of claims 1 to 5 for use in the production of ammonia from elemental substances and in the production of H from ammonia 2 and N 2 Purpose.

8. A method of using the catalytic composition according to any one of claims 1 to 5 to produce a catalyst from elemental substances N at reaction conditions below 200 bar and below 300°C. 2 and H 2 Generate NH 3 method.

9. The process according to claim 8, wherein the process is carried out at a pressure below 30 bar and below 200°C.

10. A method of using the catalytic composition according to any one of claims 1 to 5, under reaction conditions below 200 bar and below 300° C., comprising: 2 A method for generating organic nitrogen compounds such as nitriles, amines, pyrroles, pyridines, cyclic pyrroles and cyclic pyridines with alkenes or alkynes.

11. The process according to claim 10, wherein the coupling reaction is hydrogenation of one or more carbon-carbon multiple bonds of an olefin or alkyne.

12. A method of using the catalytic composition according to any one of claims 1 to 5 to denitrify organic nitrogen compounds into N 2 or ammonia and an organic product with a lower nitrogen content.

13. A method of converting organic nitrogen compounds such as nitrile, amine, pyrrole, pyridine, cyclic pyrrole and cyclic pyridine into N 2 and hydrocarbon methods.

14. A basic vanadium complex or an alkaline earth metal vanadium complex having at least two 4,5-bis(o-hydroxyphenyl)imidazole-derived substituents at a central linker module, which catalyzes the N-N bond reduction of coordinated vanadium(IV) or the oxidation of two nitrides of coordinated vanadium(V) or both, M=Li, Na, K, MgX, CaX; preferably lithium L=NH 2 NH 3 or free coordination site [V] = vanadium ion with another oxide, alkoxide, phenolate, nitride, imide, amide or ammine ligand. R 1 = alkyl, aryl, silyl, heteroaryl R 2 =H, alkyl, aryl, silyl, heteroaryl linking group = a molecular fragment containing a thermally stable CC, CN, CO, C-Si or CP bond and covalently linking two or more imidazole groups as shown. General examples are alkylsilanes, arylsilanes, alkylarylsilanes, aryl ethers, arylamines, arylphosphines, arylphosphine oxides, alkanes and cycloalkanes, aromatic and heteroaromatic systems, cyclic aromatic and cyclic heteroaromatic systems. Specific examples are m-phenylene, 3,3'-biphenylene and 1,3-adamantyl.

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