Benchmarking of Halogen Bond Strength in Solution with Nickel Fluorides: Bromine versus Iodine and Perfluoroaryl versus Perfluoroalkyl Donors

The energetics of halogen bond formation in solution have been investigated for a series of nickel fluoride halogen bond acceptors; trans-[NiF(2-C₅NF₄)(PEt₃)₂] ( A1 ), trans-[NiF{2-C₅NF₃(4-H)}(PEt₃)₂] ( A2 ), trans-[NiF{2-C₅NF₃(4-NMe₂)}(PEt₃)₂] ( A3 ) and trans-[NiF{2-C₅NF₂H(4-CF₃)}(PCy₃)₂] ( A4 ) with neutral organic halogen bond donors, iodopentafluorobenzene ( D1 ), 1-iodononafluorobutane ( D2 ) and bromopentafluorobenzene ( D3 ), in order to establish the significance of changes from perfluoroaryl to perfluoroalkyl donors and from iodine to bromine donors. ¹⁹F NMR titration experiments have been employed to obtain the association constants, enthalpy, and entropy for the halogen bond formed between these donor-acceptor partners in protiotoluene. For A2 – A4 , association constants of the halogen bonds formed with iodoperfluoroalkane ( D2 ) are consistently larger than those obtained for analogous complexes with the iodoperfluoroarene ( D1 ). For complexes formed with A2 – A4 , the strength of the halogen bond is significantly lowered upon modification of the halogen donor atom from I (in D1 ) to Br (in D3 ) (for D1 : 5≤K₂₈₅≤12 m ⁻¹, for D3 : 1.0≤K₁₉₃≤1.6 m ⁻¹). The presence of the electron donating NMe₂ substituent on the pyridyl ring of acceptor A3 led to an increase in −ΔH, and the association constants of the halogen bond complexes formed with D1 – D3 , compared to those formed by A1 , A2 and A4 with the same donors.     

Vibrational spectra and structures of CCl2 and SiCl2 molecules stabilized in an Ar matrix

Conclusions A study has been made of the isotopic structures of the ₁ and ₃ IR absorption bands of dichlorocarbene and dichlorosilylene, each stabilized in an Ar matrix at 15–20°K. A determination has been made of the valence angles, force constants, and vibration frequencies, ₁, ₂, and ₃ for various isotopic CCl₂ and SiCl₂ molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2236–2242, October, 1977.The authors would like to thank S. P. Kolesnikov and B. L. Perl'mutter who supplied the C₄H₈O₂·GeCl₂ complex, and E. A. Chernyshev, N. G. Komalenkova and S. A. Bashkirova who supplied the Si₂Cl₆.     

Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n=3, 4, 5 and 6)

Hydrazinium 2,n-pyridinedicarboxylates of general compositions N₂H₅HA, (N₂H₅)₂A·H₂O and N₂H₅HA·H₂A, where H ₂ A=2,n-pyridinedicarboxylic acid (n=3, quinolinic acid;n=4, lutidinic acid; n=5, isocinchomeronic acid and n=6, dipicolinic acid) have been prepared by the neutralisation of aqueous solution of hydrazine hydrate with the respective acids, in stoichiometric ratios. Formation of these hydrazinium derivatives has been confirmed by analytical, IR spectral and thermal studies. Among these, the monohydrazinium salts are anhydrous whereas the dihydrazinium salts are monohydrated. While lutidinic and dipicolinic acids form all the three types of salts, the quinolinic and isocinchomeronic acids do not form N₂H₅HA·H₂A and N₂H₅HA, respectively, except the other two types. Infrared spectra of these salts reveal N-N stretching frequencies of the hydrazinium ion in the region 970-950 cm^-1. The simultaneous TG and DTA of these salts show that all of them decompose without clear melting and lose hydrazine endothermically between 200 and 280°C, except dihydrazinium isocinchomeronate monohydrate in which half of the hydrazine molecule is lost exothermically, to give pyridinemono- or dicarboxylic acid intermediate which further decomposes exothermically to gaseous products. This revised version was published online in August 2006 with corrections to the Cover Date.     

A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second-Harmonic Generation and a High Laser-Induced Damage Threshold (A=Ba,Sr)

Structural modulations have been recently found to cause some unusual physical properties, such as superconductivity or charge density waves; however, thus-induced nonlinear optical properties are rare. We report herein two unprecedented incommensurately modulated nonlinear optical sulfides exhibiting phase matching behavior, A₂SnS₅ (A=Ba, Sr), with the (3+1)D superspace groups P2₁2₁2(00γ)00s or P2₁(α0γ)0, featuring different modulations of the [Sn₂S₇]_∞ belts. Remarkably, Ba₂SnS₅ exhibits an excellent second harmonic generation (SHG) of 1.1 times that of the benchmark compound AgGaS₂ at 1570 nm and a very large laser-induced damage threshold (LIDT) of 8×AgGaS₂. Theoretical studies revealed that the structural modulations increase the distortions of the Sn/S building units by about 44 or 25 % in A₂SnS₅ (A=Ba, Sr), respectively, and enhance significantly the SHG compared with α-Ba₂SnSe₅ without modulation. Besides, despite the smaller E_g, the A₂SnS₅ samples exhibit higher LIDTs owing to their smaller thermal expansion anisotropies (Ba₂SnS₅ (1.51)<Sr₂SnS₅ (2.08)<AgGaS₂ (2.97)).     

Coordination of a mesogenic Schiff-base with Mn, Co, Ni, Cu and Zn: Synthesis, spectral studies and crystal structures

A novel mesogenic (nematic) Schiff-base, N,N′-di-4-(4′-pentyloxybenzoate)salicylidene diaminoethane, H₂dpbsde (abbreviated as H₂L⁵) was synthesized and its structure studied. The Schiff-base crystallizes in the non-centrosymmetric space group Pna2₁ with Z = 4, and the mesogenic isomorphous nickel and copper complexes, [NiL⁵]₂ and [CuL⁵], in the centrosymmetric space group P2₁/c with Z = 4. The (L⁵)²⁻ species coordinates to the metal ions through two phenolate oxygens and two azomethine nitrogens. Both the [NiL⁵]₂ and [CuL⁵] complexes involve cis-MN₂O₂ planes; the former complex has a low-spin distorted square-pyramidal geometry with a Ni–Ni bonding of 3.337 Å and the latter, a square-planar geometry.     

Ternary Rhodium Borides A3Rh5B2 (A = Mg,Sc) and Quaternary Derivatives A2MRh5B2. Preparation,Crystal Structure (M = Main Group and 3 d Elements), and Magnetism (M = Mn,Fe)

The new ternary rhodium borides Mg₃Rh₅B₂ and Sc₃Rh₅B₂ (P4/mbm, Z = 2; a = 943.4(1) pm, c = 292.2(1) pm and a = 943.2(1) pm, c = 308.7(1) pm, respectively) crystallize with the Ti₃Co₅B₂ type structure. Mg and Sc may in part be substituted by a variety of elements M. For M = Si and Fe, homogeneity ranges were found according to A_3–xM_xRh₅B₂ with 0 ≤ x ≤ 1.0 for A = Sc and with x up to 1.5 for A = Mg. Quaternary compounds with x = 1 (A₂MRh₅B₂: A/M in short) were prepared with M = Be, Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Sn (Co, Ni only with A = Mg; Sn only with A = Sc; P, As with deficiencies). Single crystal X‐ray investigations show an ordered substitutional variant of the Ti₃Co₅B₂ type in which the M atoms are arranged in chains along [001] with intrachain and interchain M–M distances of about 300 pm and 660 pm, respectively. Measuring the magnetisation (1.7 K–800 K) of the phases Mg/Mn, Sc/Mn, Mg/Fe, and Sc/Fe reveals antiferromagnetic interactions in the first and dominating ferromagnetic intrachain interactions in the remaining ones. Interchain interactions of antiferromagnetic nature are evident in Sc/Mn and Mg/Fe leading to metamagnetism below T_N = 130 K, while Sc/Fe behaves ferromagnetically below T_C = 450 K. The overall trend towards stronger ferromagnetic interactions with increasing valence electron concentration is obvious.     

Synthesis and characterization of mono- and bicyclic heterocyclic derivatives containing 1,2,4-triazole, 1,3,4-thia-, and -oxadiazole rings

A series of new N- and S-substituted 1,3,4-oxadiazole derivatives were synthesized. 5-Pyridin-3-yl-3-[2-(5-thioxo-4,5-dihydro-l,3,4-thiadiazol-2-yl)ethyl]-1,3,4-oxadiazole-2(3H)-thione and 5-[(5-(pyridin-3-yl)-1,3,4-oxadiazol-2-ylthio)methyl]-N-phenyl-1,3,4-thiadiazol-2-amine were formed by cyclization of 3-(5-pyridin-3-yl-2-thioxo-1,3,4-oxadiazol-3(2H)-ylpropanimidohydrazide and 2-[(5-pyridin-3-yl-1,3,4-oxadiazol-2-yl)thio]thiosemicarbazide with CS₂ and H₂SO₄. On the other hand, a number of new bicyclic 1,2,4-triazolo[3,4-b][1,3,4]thiadiazole derivatives were synthesized. 6-Pyridin-3-ylbis[1,2,4]‐triazolo[3,4-b:4′,3′-d][1,3,4]thiadiazole-3(2H)-thione was synthesized by reaction of 6-(hydrazino)-3-pyridine-3-yl[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole with CS₂/KOH/EtOH. The structures of the newly synthesized compounds were elucidated by the spectral and analytical data IR, Mass, and ¹H NMR spectra. Correspondence: Adel A.-H. Abdel-Rahman, Department of Chemistry, Faculty of Science, Menoufia University, Shebin El-Koam, Egypt; Wael A. El-Sayed, National Research Centre, Department of Photochemistry, Cairo, Egypt.     

Coordination polyhedra of eight-coordinate zirconium complexes and a network built up by crisscross Cl...Cl contacts

Two bis(quadridentate) eight-coordinate zirconium complexes, Zr(5-Cldse)₂ (1) [5-Cldse = N,N′-di(5-chlorosalicylidene)ethylenediamino] and Zr(pida)₂ (2) [pida = N-(2-pyridylmethyl) iminodiacetato], have been prepared and crystallographically characterized. A distorted dodecahedron of N₄O₄ atoms has been found for the zirconium(IV) center of complexes (1) and (2). A network is constructed in the crystalline state of (1) by crisscross intermolecular Cl...Cl contacts (3.45 and 3.43 Å), which are shorter than the sum of spherical van der Waals radii (3.50 Å).     

A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second‐Harmonic Generation and a High Laser‐Induced Damage Threshold (A=Ba,Sr)

Structural modulations have been recently found to cause some unusual physical properties, such as superconductivity or charge density waves; however, thus‐induced nonlinear optical properties are rare. We report herein two unprecedented incommensurately modulated nonlinear optical sulfides exhibiting phase matching behavior, A₂SnS₅ (A=Ba, Sr), with the (3+1)D superspace groups P2₁2₁2(00γ)00s or P2₁(α0γ)0, featuring different modulations of the [Sn₂S₇]_∞ belts. Remarkably, Ba₂SnS₅ exhibits an excellent second harmonic generation (SHG) of 1.1 times that of the benchmark compound AgGaS₂ at 1570 nm and a very large laser‐induced damage threshold (LIDT) of 8×AgGaS₂. Theoretical studies revealed that the structural modulations increase the distortions of the Sn/S building units by about 44 or 25 % in A₂SnS₅ (A=Ba, Sr), respectively, and enhance significantly the SHG compared with α‐Ba₂SnSe₅ without modulation. Besides, despite the smaller E_g, the A₂SnS₅ samples exhibit higher LIDTs owing to their smaller thermal expansion anisotropies (Ba₂SnS₅ (1.51)<Sr₂SnS₅ (2.08)<AgGaS₂ (2.97)).     

New Steroids and a New Alkaloid from the Gorgonian Isis minorbrachyblasta: Structures,Cytotoxicity, and Antilarval Activity

Two new polyoxygenated steroids, (1α,3β,7α,11α,12β)‐gorgost‐5‐ene‐1,3,7,11,12‐pentol 12‐acetate ( 1 ) and 11‐O‐acetyl‐22‐epihippuristanol ( 2 ), and a new alkaloid, 2,3,5,6,11,11b‐hexahydro‐2‐hydroxy‐1H‐indolizino[8,7‐b]indole‐2‐carboxylic acid ( 3 ), together with three known compounds, 22‐epihippuristanol ( 4 ), hippuristanol ( 5 ), and tryptamine ( 6 ), were isolated from the EtOH/CH₂Cl₂ extracts of the South China Sea gorgonian Isis minorbrachyblasta. The structures of the new compounds were determined by spectroscopic methods. Compound 1 showed weak cytotoxicity against A549, HONE1, and HeLa cancer cell lines and strong antilarval activity towards Bugula neritina larvae with an EC₅₀ value of 5.8 μg/ml. Compound 5 showed moderate cytotoxicity against A549, HONE1, and HeLa cell lines, and the epimer mixture 4 / 5 (weight ratio 3 : 2) exhibited potent cytotoxicity against A549 and HONE1 cell lines with IC₅₀ values of 4.2 and 4.8 μg/ml, which indicated that epimers 4 and 5 might have a synergistic effect on their cytotoxicity against A549 and HONE1 cell lines.     

Lamotriginium crotonate and lamotriginium salicylate ethanol monosolvate: the role of solvent molecules in the packing organization

Two lamotriginium salts, namely lamotriginium crotonate [systematic name: 3,5‐diamino‐6‐(2,3‐dichlorophenyl)‐1,2,4‐triazin‐2‐ium but‐2‐enoate, C₉H₈Cl₂N₅⁺·C₄H₅O₂⁻, (III)] and lamotriginium salicylate [systematic name: 3,5‐diamino‐6‐(2,3‐dichlorophenyl)‐1,2,4‐triazin‐2‐ium 2‐hydroxybenzoate ethanol monosolvate, C₉H₈Cl₂N₅⁺·C₇H₅O₃⁻·C₂H₅OH, (IV)] present extremely similar centrosymmetric hydrogen‐bonded A …L …L …A packing building blocks (L is lamotriginium and A is the anion). The fact that salicylate salt (IV) is (ethanol) solvated, while crotonate salt (III) is not, has a profound effect on the way these elemental units aggregate to generate the final crystal structure. Possible reasons for this behaviour are analyzed and the hypothesis raised checked against similar structures in the literature.     

Polymerization of substituted acetylenes by various rhodium catalysts: Comparison of catalyst activity and effect of additives

This research deals with comparison of the activity of various Rh catalysts in the polymerization of monosubstituted acetylenes and the effect of various amines used in conjunction with [Rh(nbd)Cl]₂ in the polymerization of phenylacetylene. A zwitterionic Rh complex, Rh⁺(nbd)[(η⁶‐C₆H₅)B^?(C₆H₅)₃] ( 3 ), was able to polymerize phenylacetylene ( 5a ), t‐butylacetylene ( 5b ), N‐propargylhexanamide ( 5c ) and n‐hexyl propiolate ( 5d ), and displayed higher activity than the other catalysts examined, that is [Rh(nbd)Cl]₂ ( 1 ), [Rh(cod)(O‐o‐cresol)]₂ ( 2 ), and Rh‐vinyl complex ( 4 ). Monomers 5a and 5c polymerized virtually quantitatively or in fair yields with all these catalysts, while monomer 5b was polymerizable only with catalyts 3 and 4 . Monomer 5d did not polymerize in high yields with these Rh complexes. The catalytic activity tended to decrease in the order of 3 > 4 > 2 > 1 . Although polymerization of 5a did not proceed at all in toluene with [Rh(nbd)Cl]₂ alone, it smoothly polymerized in the presence of various amines as cocatalysts. The polymerization rate as well as the molecular weight of polymer depended on the basicity and steric bulkiness of amines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4530–4536, 2005     

Structure and properties of Y5Mo2O12 and Gd5Mo2O12: Mixed valence oxides with structurally equivalent molybdenum atoms

Crystals of Ln₅Mo₂O₁₂ (Ln = Y, Gd) were grown by electrochemical reduction of alkali-molybdate/rare-earth oxide melts at 1075–1100°C. A single crystal of Y₅Mo₂O₁₂, used for structure determination, was found to be monoclinic with a = 12.2376(7) Å, b = 5.7177(8) Å, c = 7.4835(5) Å, β = 108.034(5)°, and Z = 2. Although the structure was refined in space group C2/m, the true space group appears to be P2₁/m. In Y₅Mo₂O₁₂, rutile-like sheets of edge-shared MoO₆ chains linked by YO₆ octahedra are interconnected with YO₇ monocapped trigonal prisms. The Mo atoms in the chains have alternating distances of 2.496 and 3.221 Å and in that respect are similar to MoO₂. However, in contrast to metallic MoO₂ both the Y and Gd compounds are n-type semiconductors with room temperature resistivities of the order of 10³ ohm-cm. Magnetic susceptibility measurements confirm the presence of one unpaired electron per Mo₂ unit. The semiconducting behavior can be explained in terms of an unfavorable bridging oxygen coordination which prevents electron delocalization through metal-oxygen pi bonding as in MoO₂.     

Isomorphism and phase transition in triferrocenylboroxine and triferrocenylborazine

The crystal structures of triferrocenyl­boroxine, [Fe₃(C₅H₅)₃(C₁₅H₁₂B₃O₃)], (I), and triferrocenyl­borazine, [Fe₃(C₅H₅)₃(C₁₅H₁₅B₃N₃)], (II), are isomorphous. At room temperature, the space group is Cmc2₁ and the mol­ecules have crystallographic m symmetry. A reversible phase transition occurs at 283 (2) K for (I) and at 263 (5) K for (II). In the low‐temperature phase, the space group of both compounds is P2₁ and the mol­ecules no longer have internal symmetry. Intermolecular C—H?π interactions are enhanced in the low‐temperature phase.     

Synthesis,crystal structure,and characterization of a new high-dimensional phosphomolybdate architecture built from silver-complex fragments and hexa-connected P2Mo5 clusters

A new 3-D organic–inorganic hybrid phosphomolybdate, [Ag(bipy)]₄(H₂P₂Mo₅O₂₃) · 3H₂O (1) (bipy = 4,4′-bipyridine) has been hydrothermally synthesized and characterized by elemental analyses, IR, TG, and fluorescent properties. Compound 1 crystallizes in the monoclinic space group C2/c with a = 23.830(5), b = 21.030(4), c = 24.501(5) Å, β = 110.38(3)°, V = 11510(4) ų, Z = 8, and R ₁ (wR ₂) = 0.0507 (0.1210). It contains unique 3-D metal organic frameworks based on silver-complex fragments and hexa-connected P₂Mo₅ clusters via covalent bonds and represents the highest connection numbers of P₂Mo₅ clusters to date.     

Preparation and Characterization of Iron Manganese Carbide by Reaction of the Oxides and Carbon in Nitrogen

Fe₂O₃, Mn₂O₃, and their mixtures are reduced by carbon in nitrogen. The product depends on manganese loading. A cohenite Fe₃C type phase is stabilized by substituting manganese into the lattice. A single phase cohenite phase solid solution Fe_3-xMn_xC is prepared for 20-50% manganese loading, and a Fe₇C₃ type phase can be obtained with manganese loading of 65-80%. The nitrogen participates in the reduction of the manganese-rich oxide mixtures. A manganese carbonitride is obtained by heating the mixture of Mn₂O₃ and carbon in nitrogen. The composition of the new compound is analyzed as Mn₂C_0.60N_0.21 and it has a hexagonal structure with a₀ = 4.778 Å and c₀ = 4.486 Å.     

Cu(I) camphor coordination polymers: Synthesis and study of the catalytic activity for cyclization of 4‐pentyn‐1‐oic acid

The number of CuCl units per camphor ligand in [{CuCl}₂L]_n was extended to three or four in [{CuCl}₃L]_n ( 2 ) or [{CuCl}₄L]_n ( 1 ). The Hartree‐Fock ab initio calculations support the polymeric structure of 1 and 2 that catalyze the cyclization of 4‐pentyn‐1‐oic acid ( A ) forming 5‐methylenedihydrofuran‐2(3H)‐one ( B ) and/or 2‐methyl‐5‐oxotetrahydrofuran‐2‐ylpent‐4‐ynoate ( C ). The catalytic activity of 1 , 2 and other polynuclear Cu(I) complexes ( 3–5 ) was evaluated under solvent free conditions and/or solution. In the absence of solvent, catalyst 2 displays the highest activity and selectivity (75.8/23.1, C to B ratio, at 5.4% loading) while 4 reaches the highest level of A → B conversion (97.5 %) in solution. Selected reactions were followed by NMR and the kinetic constants calculated. A mechanism is proposed based on the equations used for the calculations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3316–3323     

Magnetic and structural properties of trans-bis ( -isoleucine) copper(II)

A magnetic and structural characterization of single crystals of the copper derivative of the amino acid -isoleucine, Cu[NH₂(CH)₂CH₂(CH₃)₂CO₂]₂, was performed by EPR and X-ray diffraction techniques. The complex crystallizes in the orthorhombic space group Aba2, with a = 11.165(3) Å, b = 11.111(3) Å, c = 25.985(6) Å, and Z = 8. The copper ions occupy sites of point symmetry C₂. The position and peak-to-peak linewidth of the single EPR line observed were measured at 9.7 GHz and 293 K in three perpendicular planes of the sample. The gyromagnetic tensor has near axial symmetry around , with a small anisotropy in the perpendicular plane, in agreement with the orthorhombic symmetry indicated by the crystallographic results. The principal values of are g₁ = 2.0607(5), g₂ = 2.0616(5), and g₃ = 2.2619(3), with principal directions parallel to the crystal axes. The observed angular variation of the linewidth suggests a layered arrangement of the copper ions.     

基于对叔丁基杯[8]芳烃的3d-5f核簇化合物（MxThy, M=Co、Ni、Zn）的合成、结构与磁性研究

本文以对叔丁基杯[8]芳烃（H₈C₈A）为配体,在溶剂热条件下制得了3个3d-5f化合物,[Co₂Th₄（HC8A）₂O₂（OH）₂（DMF）₆]（1）、[Ni₂Th₅（H₂C8A）（C₈A）O₄（OH）₂（DMF）₅（CH₃OH）₂]（2）、[Zn₂Th₆（HC8A）（C8A）O₅（CH₃O）（C₃H₆NO₂）₂（DMF）₅（CH₃OH）]（3）（其中H₈C8A=对叔丁基杯[8]芳烃,DMF=N,N-二甲基甲酰胺）。X-射线单晶测试表明,这3个化合物均为2个以尾对尾方式排列的杯[8]芳烃分子中间夹1个3d-5f核簇的三明治型结构。杯[8]芳烃均表现为双锥式构型,且每个锥式空腔下缘结合1个钍离子,双锥的连接处及2个杯芳烃分子之间由过渡金属离子或钍离子连接。不同过渡金属离子不同的配位环境导致3种不同核簇的形成。化合物1的磁性研究表明,该化合物在低温下表现出弱铁磁性相互作用。     

Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me₂NCH₂F to the electron‐deficient phosphanes (C₂F₅)_nPF_3?n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C₂F₅)_nF_5?nP(CH₂NMe₂?CH₂NMe₂)] are converted into the corresponding phosphonium salts [(Me₃PCH₂NMe₂]⁺[(C₂F₅)_nF_5?nP(CH₂NMe₂)]^? by treatment with PMe₃. In addition [(C₂F₅)₃F₂P(CH₂NMe₂?CH₂NMe₂)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF₃ analogue. Reaction of [(C₂F₅)₃F₂P(CH₂NMe?CH₂NMe₃)] and PMe₃ gave rise to the formation of the zwitterionic phosphonium phosphate [(C₂F₅)₃F₂P(CH₂NMe?CH₂PMe₃)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs⁺[(C₂F₅)₃F₂P(CH₂NMe₂)]^? was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.