Neue Ternäre Silber(II)-fluoride: Ag3IIM2IVF14 (MIV = Zr,Hf)

New Ternary Silver (II) Fluorides: Ag M F₁₄ (M^IV = Zr, Hf) Single crystals of deeply blue violet coloured fluorides Ag₃^IIM₂^IVF₁₄ (M^IV = Zr, Hf) have been obtained by heating powder samples under F₂/N₂ (1:2) at T ≈? 600°C. The isotypic compounds crystallizes monoclinic with a = 924.9, b = 668.6, c = 907.3 pm, β = 90.30° (Ag₃Hf₂F₁₄) and a = 922.5, b = 667.6, c = 906.3 pm, β = 91.30° (Ag₃Zr₂F₁₄) (Four circle diffractometer data, Philips PW 1100), spcgr. C2/m-C_2h³ (No. 12), Z = 2. There are two different sorts of Ag²⁺:Ag(1) with coordination number C.N. [Ag(1)] = 4 + 2 and Ag(2) with C.N.[Ag(2)] = 4 + 4 against F^?. Ag(1) can be substituted by Cu²⁺, Ni²⁺, Zn²⁺, Mg²⁺ (all of blue/red violet colour), Ag(2) by Ca²⁺, Cd²⁺, Hg²⁺ (bright green). From (preliminary) powder data CuAg₂Zr₂F₁₄ with a = 912.3(4), b = 661.2(2), c = 899.4(2) pm, β = 90.70° (3) is isotypic, the other compounds seems to be of closely related type of structure.     

C−H Bond Trifluoromethylation of Arenes Enabled by a Robust,High‐Valent Nickel(IV) Complex

The robust, high‐valent Ni^IV complex [(Py)₂Ni^IVF₂(CF₃)₂] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X‐ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric Ni^IIICF₃ complexes 2 ⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X‐ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C−H bond‐breaking/C−CF₃ bond‐forming sequence can occur both at Ni^IVCF₃ and Ni^IIICF₃ centers.     

C−H Bond Trifluoromethylation of Arenes Enabled by a Robust,High‐Valent Nickel(IV) Complex

The robust, high‐valent Ni^IV complex [(Py)₂Ni^IVF₂(CF₃)₂] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X‐ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric Ni^IIICF₃ complexes 2 ⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X‐ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C−H bond‐breaking/C−CF₃ bond‐forming sequence can occur both at Ni^IVCF₃ and Ni^IIICF₃ centers.     

Dimethyl telluride as a ligand: synthesis and physicochemical studies on its complexes with transition metal bis(chlorosulphates) M(SO3Cl)2(M=Cr,Mn, Fe,Co, Ni,Cu)

Summary Dimethyl telluride, Me₂Te, reacts with first row transition metal bis(chlorosulphates), M(SO₃Cl)₂(M=Cr^II, Mn^II, Fe^II, Co^II, Ni^II, Cu^II) in MeCN resulting in the formation of compounds of the type [M(SO₃Cl)₂-(Me₂Te)₂]. These compounds are stable under N₂ but decompose on exposure to moist air. The covalent nature of bonding of the SO₃Cl^– group has been ascertained on the basis of a positive shift in ₁ (A) vibration, splitting of the doubly degenerate (E) modes and low molar conductivity values. The magnetic moments and electronic spectra suggest an octahedral geometry for these compounds (except for the Ni^II complex where a tetragonal distortion is observed) where each SO₃Cl^– group is bonded in a bidentate manner.     

MII-N-diisopropoxythiophosphorylthiobenzamide complexing processes in M2[Fe(CN)6]-gelatin-immobilized matrices (M = Co,Ni, Cu)

Complexing processes in M^II-N-diisopropoxythiophosphorylthiobenzamide binary systems (M = Co, Ni, Cu) in metal(II) hexacyanoferrate(II) gelatin-immobilized matrices upon contact with aqueous–alkaline (pH = 12.0 ± 0.1) solutions of organic compounds have been studied. It has been shown that, in Co^II and Cu^II, the initial act of complexing involves destruction of the Co^II and Cu^II hexacyanoferrates(II) by OH^– ions, leading to formation of the corresponding hydroxides which react with the ligand indicated. In the both systems, successive addition of two ligand molecules per M(OH)₂ fragment occurs and [MB(OH)(OH₂)] and [MB₂] coordination compounds are formed (B^–-a singly deprotonated ligand form). In the Ni^II-N-diisopropoxythiophosphorylthiobenzamide system, the formation of three complexes, (Ni₂BOH)₂[Fe(CN)₆], [NiB(OH)(OH₂)] and [NiB₂] occurs.     

Preparation and Characterisation of a Bis-μ-Hydroxo-NiIII2 Complex

Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-Ni^II₂ complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two Ni^II ions and two bridging hydroxide ligands. Titration of the 1 e⁻ oxidant (NH₄)₂[Ce^IV(NO₃)₆] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing Ni^IINi^III and Ni^III₂ diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-Ni^III₂ 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-Ni^III complexes reported to date.     

Zur Kenntnis des RbNiCrF6-Typs: über CsCuMF6 (M  NiIII,TiIII), CsMgMF6 (M  Co,Fe, Ga) und CsZnMF6 (M  NiIII,CoIII, FeIII)

On the RbNiCrF₆ Type(¹): On CsCuMF₆ (M?Ni^III, Ti^III), CsMgMF₆ (M ?Co, Fe, Ga), and CsZnMF₆ (M?Ni^III, Co^III, Fe^III) New prepared are the cubic compounds CsCuNi^IIIF₆ (dark brown, a = 10.14 Å); CsZnNi^IIIF₆ (dark brown, a = 10.17 Å); CsCuTi^IIIF₆ (light grey, a = 10.39 Å); CsMgGaF₆ (colourless, a = 10.23 Å); CsMgFeF₆ (colourless, a = 10.53 Å); CsZnFeF₆ (colourless, a = 10.42 Å); CsMgCo^IIIF₅ (light blue, a = 10.27 Å) and CsZnCo^IIIF₆ (light blue, a = 10.34 Å), all RbNiCrF₆-type of structure. The Madelung part of lattice energy, MAPLE, is calculated and discussed.     

Weak Antiferromagnetic Exchange and Ferromagnetic Alignment of FeII (S=2) Spins in Differently Charged {HAT ⋅ (FeIICl2)3}n (n=2- and 3-) Assemblies of Hexaazatriphenylenes (HAT)

Hexaazatrianthracene (HATA) and hexaazatriphenylenehexacarbonitrile {HAT(CN)₆} are reduced by metallic iron in the presence of crystal violet (CV⁺)(Cl⁻). Anionic ligands are produced, which simultaneously coordinate three Fe^IICl₂ to form (CV⁺)₂{HATA ⋅ (Fe^IICl₂)₃}²⁻ ⋅ 3 C₆H₄Cl₂ ( 1 ) and (CV⁺)₃{HAT(CN)_6. (Fe^IICl₂)₃}³⁻ ⋅ 0.5CVCl ⋅ 2.5 C₆H₄Cl₂ ( 2 ). High-spin (S=2) Fe^II atoms in both structures are arranged in equilateral triangles at a distance of 7 Å. An antiferromagnetic exchange is observed between Fe^II in {HATA ⋅ (Fe^IICl₂)₃}²⁻ ( 1 ) with a Weiss temperature (Θ) of −80 K, the PHI estimated exchange interaction (J) is −4.7 cm⁻¹. The {HAT(CN)₆ ⋅ (Fe^IICl₂)₃}³⁻ assembly is obtained in 2 . The formation of HAT(CN)₆^.3− is supported by the appearance of an intense EPR signal with g=2.0037. The magnetic behavior of 2 is described by a strong antiferromagnetic coupling between the Fe^II and HAT(CN)₆^.3− spins with J₁=−164 cm⁻¹ (−2 J formalism) and by a weaker antiferromagnetic coupling between the Fe^II spins with J₂=−15.4 cm⁻¹. The stronger coupling results in the spins of the three Fe^IICl₂ units to be aligned parallel to each other in the assembly. As a result, an increase of the χ_MT values is observed with the decrease of temperature from 9.82 at 300 K up to 15.06 emu ⋅ K/mol at 6 K, and the Weiss temperature is also positive being at +23 K. Thus, a change in the charge and spin state of the HAT-type ligand to ⋅3⁻ results in ferromagnetic alignment of the Fe^II spins, yielding a high-spin (S=11/2) system. DFT calculations showed that, due to the high symmetry and nearly degenerated LUMO of both HATA and HAT(CN)₆, their complexes with Fe^IICl₂ have a variety of closely lying excited high-spin states with multiplicity up to S=15/2.     

Zur Kristallstruktur von Cu2M(BO3)O2 (M = Fe3+, Ga3+)

The Crystal Structure of Cu₂M(BO₃)O₂ (M = Fe³⁺, Ga³⁺) Single Crystals of the compounds Cu₂M(BO₃)O₂ (M = Fe³⁺ (I), Ga³⁺ (II)) were obtained by a B₂O₃ flux-technique. They crystallize in a monoclinic distorted variant of a Ludwigite structure with a partly ordered metal distribution. X-ray investigations on single crystals led to the space group C–P2₁/c (No. 14); I: a = 3.108(1); b = 12.003(1); c = 9.459(3) Å; b? = 96.66(3)°; Z = 4 and II: a = 3.1146(2); b = 11.921(3); c = 9.477(2) Å; b? = 97.91(2)°; Z = 4. All metal-sites are distorted octahedraly coordinated by oxygen-ions. The structure contains isolated planar BO₃-units and oxygen which is not coordinated to boron.     

Crystal structure and magnetism of layered Ln2Ca2MnNiO8 (Ln=Pr,Nd, Sm,and Gd) compounds

We report the syntheses, crystal structure, and magnetic properties of a series of distorted K₂NiF₄-type oxides Ln₂Ca₂MnNiO₈ (Ln=Pr, Nd, Sm, and Gd) in which Ln/Ca and Mn/Ni atoms randomly occupy the K and Ni sites respectively. The Ln=La compound does not form. These compounds show systematic distortions from the ideal tetragonal K₂NiF₄ structure (space group I4/mmm) to an orthorhombic structure (space group Pccn) with buckled MO₂ (M=Mn/Ni) layers. The degree of distortion is increased as the size of Ln decreases. Based on the magnetic data and X-ray absorption near edge spectra, we assigned Mn^IV and Ni^II. The Curie–Weiss plots of the high temperature magnetic data suggest strong ferromagnetic interactions probably due to Mn^IV–O–Ni^II linkages, implying local ordering of Mn/Ni ions to form ferromangnetic clusters in the MO₂ layers. At low temperatures below 110–130 K, these compounds show antiferromagnetic behaviors because of Mn^IV–O–Mn^IV and/or Ni^II–O–Ni^II contacts between the ferromagnetic clusters. The Ln=Pr and Nd compounds show additional antiferromagnetic signals that we attribute to the interlayer interactions between the clusters mediated by the Pr³⁺ and Nd³⁺ ions in the interlayer spaces. The present compounds show many parallels with the previously reported Ln₂Sr₂MnNiO₈ compounds.     

Cs2Cu3MIVF12 (MIV = Zr,Hf) – Kristallstruktur und magnetische Eigenschaften

Cs₂Cu₃M^IVF₁₂ (M^IV = Zr, Hf) – Crystal Structure and Magnetic Behaviour Colourless single crystals of Cs₂Cu₃ZrF₁₂ are obtained by heating the binary fluorides in sealed Pt-tubes under dry argon (solid state reaction, T ≈? 700°C, t ≈? 7–10 d). The compound crystallizes trigonal-rhomboedrical in the space group R3 m-D (Nr. 166); lattice parameters are a = 716.61(6) pm, c = 2 046.4(2) pm, Z = 3 (Four cycle diffractometer data, AED 2). The structure is dominated by layers of corner-sharing, Jahn-Teller-distorted [CuF₆]-Octahedra, which are connected via regular [ZrF₆]-Octahedra to stackings parallel [00.1]. Cs⁺-ions are located in the spacings of the octahedra-network. From powder data Cs₂Cu₃HfF₁₂ with a = 716.32(4) pm, c = 2 048.6(2) pm is isotypic. Both compounds show antiferromagnetic behaviour already at temperatures about 200 K.     

Synthesis, crystal structures and magnetic properties of M(II)Cu(II) chains (M = Mn and Co) with sterically hindered alkyl-substituted phenyloxamate bridging ligands

A series of neutral oxamato‐bridged heterobimetallic chains of general formula [MCu(L^x)₂(S)₂] ? p S ? q H₂O [p=0–1, q=0–2.5; L¹=N‐2,6‐dimethylphenyloxamate, S=DMF with M=Mn ( 1 a ) and Co ( 1 b ); L²=N‐2,6‐diethylphenyloxamate, S=DMF with M=Mn ( 2 a ) and Co ( 2 b ) or S=DMSO with M=Mn ( 2 c ) and Co ( 2 d ); L³=N‐2,6‐diisopropylphenyloxamate, S=DMF with M=Mn ( 3 a ) and Co ( 3 b ) or S=DMSO with M=Mn ( 3 c ) and Co ( 3 d )] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L^x)₂]^2? (x=1–3) with M²⁺ cations (M=Mn and Co) in DMF or DMSO as the solvent. The single‐crystal X‐ray structures of 2 a and 3 a reveal the occurrence of well‐isolated, zigzag, oxamato‐bridged manganese(II)–copper(II) chains. The intrachain Cu ??? Mn distances across the oxamato bridge are 5.3761(7) and 5.4002(17) Å for 2 a and 3 a , respectively, whereas the shortest interchain Mn ??? Mn distances are 9.4475(16) and 8.1649(14) Å for 2 a and 3 a , respectively. All of these M^IICu^II chains (M=Mn and Co) exhibit 1D ferrimagnetic behaviour with moderately strong intrachain antiferromagnetic coupling between the square‐planar Cu^II and octahedral high‐spin M^II ions across the oxamato bridge [?J=31.4–35.2 and 33.4–44.8 cm^?1, respectively; H =∑_i?J S _M,i( S _Cu,i+ S _Cu,i?1)]. Only the Co^IICu^II chains show slow magnetic relaxation effects characteristic of single‐chain magnets (SCMs). Analysis of the magnetic relaxation dynamics of 3 d shows a thermally activated mechanism (Arrhenius law dependence) with values of the pre‐exponential factor (τ₀=2.6×10^?9 s) and activation energy (E_a=7.7 cm^?1) that are typical of SCMs. In contrast, two relaxation regimes are observed for 2 d in different temperature regions (τ₀=3.2×10^?10 s and E_a=24.7 cm^?1 for T<4.5 K and τ₀=3.2×10^?14 s and E_a=37.5 cm^?1 for T>4.5 K).     

Solvothermal Syntheses and Characterization of Thiostannates [M(en)3]2Sn2S6 (M = Mn,Co, Zn), the Influence of Metal Ions on the Crystal Structure

Three new thiostannates [M(en)₃]₂Sn₂S₆ (en = ethylenediamine, M = Mn( 1 ), Co( 2 ) and Zn( 3 )) were synthesized by solvothermal method. The crystals were grown up in a Teflon‐lined steel autoclave at temperature about 180 °C. All the three compounds consist of discrete [Sn₂S₆]^4— anions, which are dimer of two tetrahedral SnS₄ sharing a common edge. The transition metal cations are six‐coordinated by three ethylenediamine molecules forming octahedral complex ions. Although the synthetic procedures, the mole ratio of the reactants and the solvent are essentially the same, the compound of Mn^II is quite different in structure from that of compounds of Co^II and Zn^II. Compound 1 crystallizes in monoclinic crystal system, C2/c, whereas compounds 2 and 3 crystallize in the orthorhombic crystal system, Pbca. Unlike compound 1 , the [M(en)₃]²⁺ cations in 2 and 3 are disordered. The difference of molecular packing between 1 and 2 ‐ 3 is considered due to the influence of the entities of the metal ions, such as radii and the coordination properties. The thermal chemical behaviors of the compounds 1 ‐ 3 were discussed and the results are also related to the property of the metal ions.     

Synthesis,spectral and magnetic studies on mixed-ligand complexes M(DIAFO)2(NCS)2 and M(DIAFH)2X2 (M = FeII,CoII, NiII). The crystal structure of Co(DIAFO)2(NCS)2

Summary A series of mixed-ligand complexes of group VIII metals, M(DIAFO)₂(NCS)₂ and M(DIAFH)₂X₂ (M = Fe^II, Co^II, Ni^II, X = NCS^–, Cl^–) with the 3,3-bridged derivative of 2,2-bipyridyl (bipy) (1) were prepared, where DIAFO (2) and DIAFH (3) are 4,5-diazafluoren-9-one and 4,5-diazafluoren-9-hydrazone, respectively. These complexes were investigated by i.r., u.v.-vis-near i.r. spectroscopy and by variable-temperature magnetic susceptibility measurements. The electronic spectra show that the two ligands exert a field strength far removed from the Fe^II cross-over value. All the complexes are paramagnetic, following the Curie-Weiss law in the 77–300 K range. A typical crystal structure of Co(DIAFO)₂(NCS)₂ for these compounds was determined with orthorhombic, space group Pcan, a = 10.377(5) Å, b = 13.289(6) Å, c= 16.629(7) Å, V = 2293(2) ų, D _c = 1.563 g cm^–3, F(000) = 1091.74, Z = 4, R = 0.043, R = 0.047. Steric effects are thought to be operative in both ligands studied, but are weaker than those of the typical bidentate diimine ligand bipy.Author to whom all correspondence should be directed.     

Cyanido-bridged one-dimensional systems assembled from [ReIVCl4(CN)2]2? and [MII(cyclam)]2+ (M = Ni, Cu) precursors

Three new cyanido-bridged heterometallic Re^IVNi^II and Re^IVCu^II one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [Re^IVCl₄(CN)₂]^2? and [M^II(cyclam)]²⁺ (M = Ni in 1, Cu in 2) or [Cu^II(N,N??-dimethylcyclam)]²⁺ (in 3) building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 Re^IV centers and the 3d metal ions: S = 1 Ni^II or S = 1/2 Cu^II. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions (antiferromagnetic for 1 and 2; canted antiferromagnetic for 3) is detected for the three compounds.     

Drei Heterocubanartige (MII4O4)‐Typ Verbindungen (M = FeII,CoII, NiII)

By reaction of M^IICl₂·x H₂O (M = Fe (x = 4), Co, Ni (x = 6)) and LiOH·H₂O in diethylene glycol (DEG) rod‐like crystals of the composition M^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ are formed. According to X‐ray diffraction data obtained by both, single crystals and powders, the Co^II and Ni^II compounds crystallize monoclinic with C2/c (Co^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 1 ): a = 2084.1(4), b = 919.0(2), c = 1754.0(4) pm, β = 124.3(1)°, Z = 4; Ni^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 2 ): a = 2055.2(4), b = 932.1(2), c = 1727.4(4) pm, β = 125.2(1)°, Z = 4), whereas Fe^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 3 ) crystallizes tetragonal with (a = 1251.4(2), c = 915.3(2) pm, Z = 2). All compounds exhibit analogous molecular structures which are built of a heterocubane‐type core consisting of four metal ions and four deprotonated oxygen atoms of four coordinated diethylene glycol molecules. Neutrality of charge is realized by additional coordination of four chloride anions. In addition to the structural characterization, the thermal and magnetical properties of the title compounds are investigated in detail.     

2-Aminoacetophenone-2-thenoylhydrazone complexes of bivalent 3d metal ions

Summary 2-Aminoacetophenone-2-thenoylhydrazone, Haath, C₄H₃SC(O)NHN=C(Me)C₆H₄NH₂-o, forms complexes with metal(II) salts of empirical compositions [VO(Haath)₂SO₄], [M(Haath)₂Cl₂] [M=Co^II, Ni^II, Cu^II or Zn^II] and [M(aath)₂] [M=V^IVO, Co^II, Ni^II, Cu^II or Zn^II] which have been characterized by elemental analyses, molar conductance, magnetic susceptibility, electronic, e.s.r., i.r. and n.m.r. (¹H and¹³C) spectral studies. X-ray and electron diffraction patterns have been obtained in order to elucidate the structure of the Cu^II complexes. Photoacoustic spectra of powder Ni^II complexes have been recorded and interpreted in the light of u.v./vis. spectra.     

Contributions on Thermal Behaviour and Crystal Chemistry of Anhydrous Phosphates. XXXIV [1] Oxygen Equilibrium Pressures in Ternary Systems M / P / O (M = Co,Ni) and Heats of Formation of Anhydrous Cobalt(II) and Nickel(II) Phosphates

Oxygen equilibrium pressures have been measured in the temperature range 800 °C to 1000 °C by coulometric/potentiometric techniques for several equilibrium regions in the ternary systems M / P / O (M = Co, Ni). In both systems oxygen coexistence pressures of three‐phase equilibrium solids phosphide/phosphate are about 3 to 5 orders of magnitude smaller than p(O₂) above the corresponding M_s / MO_s system. Heats of formation Δ_fH°₂₉₈ and standard entropies S°₂₉₈ for the phosphates have been obtained from 2^nd and 3^rd law evaluation of the temperature dependence of the oxygen coexistence pressures. Thermodynamic data from literature for the phosphides of cobalt and nickel and estimated heat capacities for the anhydrous phosphates Co₃(PO₄)₂, Co₂P₂O₇, Ni₃(PO₄)₂, Ni₂P₂O₇ and Ni₂P₄O₁₂ were used for these calculations. Thus obtained enthalpies and entropies are compared to results from thermodynamic modelling of observed solid phase equilibria in the ternary systems M / P / O (M = Co, Ni).     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%