Synthesis,Crystal Structure,and Magnetic Properties of (2,2′‐dipyridylamine)(X−) Copper(II) Complexes (X−: Cyanate,Dicyanamide, Acetate,Thiocyanato)

The synthesis, structure, and magnetic properties of four 2,2′‐dipyridylamine ligand (abbreviated as Hdpa) containing copper(II) complexes. There is one binuclear compound, which is [Cu₂(μ_1,1‐NCO)₂(NCO)₂(Hdpa)₂] ( 1 ), and three mononuclear compounds, which are [Cu{N(CN)₂}₂(Hdpa)₂] ( 2 ), [Cu(CH₃CO₂)(Hdpa)₂·N(CN)₂] ( 3 ), and [Cu(NCS)(Acac)] ( 4 ). Compounds 1 and 4 crystallize in the monoclinic system, space group P2(1)/c and Z = 4, with a = 8.2465(6) Å, b = 9.3059(7) Å, c = 16.0817(12) Å, β = 91.090(1)°, and V = 1233.90(16) ų for 1 and a = 7.6766(6) Å, b = 21.888(3) Å, c = 10.4678(12) Å, β = 90.301(2)°, and V= 1758.8(4) ų for 4 . Compounds 2 and 3 crystallize in the triclinic system, space group P‐1 and Z = 1, with a = 8.1140(3) Å, b = 8.2470(3) Å, c = 9.3120(4) Å, β = 102.2370(10)°, and V = 592.63(4) ų for 2 and a = 7.4780(2) Å, b = 12.5700(3) Å, c = 13.0450(3) Å, β = 96.351(2)°, and V = 1211.17(5) ų for 3 . Complex ( 1 ), the magnetic data was fitted by the Bleaney‐Bowers equation (1). A very good fit was derived with J = 23.96, Θ = ?1.5 (g = 1.97). Complex ( 1 ) shows the ferromagnetism. Complexes ( 2 ), ( 3 ) and ( 4 ) of have the it is the typical paramagnetic behavior of unpaired electrons. Under a low temperature around 25 K, complexes ( 2 ) and ( 3 ) show weak ferromagnetic behavior. They are the cause of hydrogen bonds.     

Synthesis of two novel cobalt complexes and their crystal structures

Two new cobalt complexes were successfully synthesized from the reaction of binaphthyl Schiff base 2 with Co(OAc)₂ in the presence of sodium methoxide at 80 °C for 24 h and Co(acac)₃ in toluene under reflux. Their unique crystal structures are unambiguously disclosed by X‐ray analysis. Complex 3 is triclinic, space group P1 , unit cell dimensions a = 10.742(2) Å, b = 11.153(2) Å, c = 12.715 Å, α = 79.865(3) °, β = 76.053 °, γ = 72.532(4) °, volume 1401.3(5) ų, Z = 2. Complex 4 is triclinic, space group P1 , unit cell dimensions a = 10.801(2) Å, b = 12.554(3) Å, c = 15.219(3) Å, α = 105.672(4) °, β = 103.048 °, γ = 104.594(4) °, volume 1824.8(7) ų, Z = 2, calculated density 1.428 Mg m⁻³. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and Structure of η4-Enone Complexes of Ruthenium(0)

A variety of [Ru(CO)₂L(η⁴enone)] complexes (L = phosphines, phosphites, and arsines, enone = (E)-4-phenylbut-3-en-2-one) have been synthesized. ¹H-, ¹³C-, and ³¹P-NMR spectra are reported and the X-ray structures of two Ru complexes with L ? Ph₃P(7), Et₃P ( 10 ) and one Fe complex with L ? Ph₃P ( 14 ) are presented. All three compounds crystallize in the same monoclinic space group P2₁/n with a = 10.575(2) Å, b =9.213(2) Å, and c = 27.608(5) Å, β = 100.04(2)°, Z = 4 for 7 , a = 10.276(3) Å, b = 12.935(3) Å, and c = 14.854(2) Å, β = 96.96(2)°, Z = 4 for 10 , and a = 10.492(2) Å, b = 9.232(3) Å, and c = 27.129(3) Å, β = 98.67(2)°, Z = 4 for 14 . The structures of the Ru complexes are compared with the Fe analogues. In the case of M ? Ru and L ? (EtO)₃P, (MeO)₃P, and (i-PrO)₃P ( 9 , 11 , and 13 , respectively) stereoisomers could be detected by ³¹P-NMR at room temperature, wich arise from rotation at the coordinated metal centre.     

Intermetallic Phases in the Ca‐Cu‐Sn System

Twelve ternary alloys in the Ca‐Cu‐Sn system were synthesized as a test on the existing phases. They were prepared from the elements sealed under argon in Ta crucibles, melted in an induction furnace and annealed at 700 °C or 600 °C. Four ordered compounds were found: CaCuSn (YbAuSn type), Imm2, a = 4.597(1) Å, b = 22.027(2) Å, c = 7.939(1) Å, Z = 12, wR2 = 0.080, 1683 F² values; Ca₃Cu₈Sn₄ (Nd₃Co₈Sn₄ type), P6₃mc, a = 9.125(1) Å, c = 7.728(1) Å, Z = 2, wR2 = 0.087, 704 F² values; CaCu₂Sn₂ (new structure type), C2/m, a = 10.943(3) Å, b = 4.222(1) Å, c = 4.834(1) Å, β = 107.94(1)°, Z = 2, wR2 = 0.051, 343 F² values; CaCu₉Sn₄ (LaFe₉Si₄ type), I4/mcm, a = 8.630(1) Å, c = 12.402(1) Å, Z = 4, wR2 = 0.047, 566 F² values. In all phases the shortest Cu‐Sn distances are in the range 2.59‐2.66Å, while the shortest Cu‐Cu distances are practically the same, 2.53‐2.54Å, except CaCuSn where no Cu‐Cu contacts occur.     

Structural Aspect of CuCN Catalytic Cyclodimerization of N‐Allylquinolinium Halides

By a reaction between the corresponding [N‐allylquinolinium]X (X = Cl, Br, I) and CuCN in a methanolic medium crystals of [C₂₄H₂₁N₂][CuCl_1.35Br_0.65] ( 1 ), [C₂₄H₂₁N₂][CuBr₂] ( 2 ) and [C₂₄H₂₁N₂]I ( 3 ) have been obtained and characterized structurally by X‐ray (at 100 K). Isostructural complexes 1 and 2 crystallize in monoclinic space group P2₁/n, Z = 4: 1 a = 13.193(4), b = 19.185(5), c = 8.429(3), β = 104.85(3)°, V = 2062(1) ų, R = 0.051 for 3359 reflections; 2 a = 13.373(4), b = 19.104(6), c = 8.544(3) Å, β = 104.58(3)°, V = 2112(1) ų, R = 0.057 for 3297 reflections. Compound 3 crystallizes in monoclinic system, space group P2₁/n, Z = 4, a = 8.889(2), b = 16.842(3), c = 13.294(3) Å, β = 104.71(3)° V = 1925(1) ų, R = 0.034 for 4042 reflections. The same cation [C₂₄H₂₁N₂]⁺ in the compound 1 – 3 appeared as a product of N‐allylquinolinium catalytic cyclodimerization. Neither N‐allyl nor C‐vinyl groups participate in Cu^I π‐coordination in the structures of 1 and 2 , therefore [CuX₂]^? anions can possess a linear form.     

Structures and Properties of Novel Mononuclear Iron(III) Complexes with Benzimidazole Containing Tripodal Tetradentate Ligands

The iron(III) complexes of the tripodal benzimidazole‐containing ligands tris(2‐benzimidazolylmethyl)amine (ntb), bis(2‐benzimidazolylmethyl)(2‐hydroxyethyl)‐amine (bbimae) and tris(5,6‐dimethyl‐2‐benzimidazolylmethyl)amine (me₂ntb) are structural and functional models for intradiol cleaving catechol dioxygenases. The complexes [Fe(ntb)Cl₂]Cl · 3 CH₃OH ( 1 ; P 1, a = 9.830(2) Å, b = 12.542(3) Å, c = 13.139(3) Å, α = 82.88(3)°, β = 73.45(3)°, γ = 85.53(3)°, V = 1539.2(6) ų; Z = 2) and [Fe(bbimae)Cl₂]Cl ( 2 ; P2₁/n, a = 7.461(2) Å, b = 18.994(5) Å, c = 14.515(4) Å, β = 98.22(2)°, V = 2035.8(9) ų, Z = 4) have been characterized by X‐ray crystallography and spectroscopic methods. In the octahedrally coordinated complexes two cis coordination sites – essential for catechol binding – are occupied by chloride ligands. The significant intradiol cleaving catechol dioxygenase activity of the model complexes was examined using 3,5‐di‐tert‐butylcatechol as a substrate.     

Alkyl Rearrangement of Derivatives of 2-Anilino-4,6-dialkoxy-1,3,5-triazines in the Solid- and Liquid-state

Abstract

2-Anilino-4,6-dimethoxy-1,3,5-triazine (13), 2-anilino-4,6-diethoxy-1,3,5-triazine (14), 2-(2′-nitoanilino) 4,6-dimethoxy-1,3,5-triazine (15) undergo alkyl rearrangement in the liquid-state, while 2-(4′-nito-anilino) 4,6-dimethoxy-1,3,5-triazine (16) undergoes methyl rearrangement in the solid-state. The crystal structure and thermal behavior of these compounds are described. 13 crystallizes in monoclinic P2₁/c space group, a = 11.030(4), b = 6.345(4), c = 16.315(4) Å, β = 90.76(3)°. The calculated density for Z = 4 is 1.351 Mg/m³. The number of unique reflections collected is 2092, and the final R = 0.0643 [I > 2σ(I)]. 14 crystallizes in triclinic P-1 space group, a = 7.700(2), b = 9.723(3), c = 10.154(3) Å, α = 78.78(3), β = 70.32(3), γ = 73.67(3)°. The calculated density for Z = 2 is 1.266 Mg/m³. The number of unique reflections collected is 2401, and the final R = 0.0561 [I > 2σ(I)]. 15 crystallizes in monoclinic P21/m space group, a = 11.020(3), b = 6.600(2), c = 8.409(3) Å, β = 99.72(3)°. The calculated density for Z = 2 is 1.527 Mg/m³. The number of unique reflections collected is 1153, and the final R = 0.0502 [I > 2σ(I)]. 16 crystallizes in monoclinic P21/c space group, a = 7.499(3), b = 21.846(5), c = 7.895(3) Å, β = 115.42(3)°. The calculated density for Z = 4 is 1.576 Mg/m³. The number of unique reflections collected is 2036, and the final R = 0.0757 [I > 2σ(I)].     

Synthesis and study of ammonium decamolybdodimetallates

Ammonium decamolybdodimetallates (NH₄)_n[M₂Mo₁₀O₃₄(OH)₄] · 7H₂O, where M = Cr³⁺ (n = 6), Cu²⁺ (n = 8), or Ni²⁺ (n = 8), were synthesized for the first time and studied by X-ray diffraction, thermogravimetry, and IR spectroscopy. The compounds crystallize in the triclinic system with the following unit cell parameters: a = 10.68(2) Å, b = 9.46(2) Å, c = 7.97(2) Å, α = 75.12(3)°, β = 96.82(3)°, γ = 102.21(3)°, V = 754.4(3) ų, ρ_calcd = 4.05 g/cm³, Z = 1 for the chromium compound; and a = 10.57(2) Å, b = 9.29(2) Å, c = 8.47(2) Å, α = 73.91(3)°, β = 96.05(3)°, γ = 104.71(3)°, V = 854.3(3) ų, ρ_calcd = 3.68 g/cm³, Z = 1 (for the copper compound); and a = 10.96(2) Å, b = 8.95(2) Å, c = 7.40(2) Å, α = 71.76(3)°, β = 97.04(3)°, γ = 102.91(3)°, V = 875.3(3)ų, ρ_calcd = 3.65 g/cm₃, Z = 1 for the nickel compound.     

The Structure of Hydrotris(imidazolyl)boratothallium(I) – the First Structurally Authenticated Tris(imidazolyl)borate Metal Complex

The title compound crystallizes in the monoclinic space group P2₁/n with a = 8.706(1), b = 9.192(1), c = 15.261(2) Å, β = 94.740(3)°, V = 1217.0(3) ų, Z = 4, D_calc = 2.278 g cm^–3. The tris(imidazolyl)borate ligand bridges between three thallium atoms. The structure consists of one‐dimensional twisted ladder‐like strands.     

Neue Hexachalcogeno‐Hypodiphosphate der Erdalkalimetalle und des Europiums

New Hexachalcogeno‐Hypodiphosphates of Alkaline‐Earth Metals and Europium Six hexathio‐ and hexaseleno‐hypodiphosphates respectively with the formula M₂P₂X₆ (M = Ca, Sr, Eu, Ba; X = S, Se) were prepared by heating the elements at 750 °C (60 h) and their crystal structures were determined by single crystal X‐ray methods. Eu₂P₂S₆ (a = 9.396(2), b = 7.531(2), c = 6.593(2) Å, β = 91.48(2) °), Ba₂P₂S₆ (a = 9.966(1), b = 7.580(2), c = 6.737(2) Å, β = 91.17(3) °), Ca₂P₂Se₆ (a = 9.664(2), b = 7.519(2), c = 6.859(1) Å, β = 92.02(3) °), Sr₂P₂Se₆ (a = 9.844(2), b = 7.788(2), c = 6.963(1) Å, β = 91.50(3) °), Eu₂P₂Se₆ (a = 9.779(2), b = 7.793(2), c = 6.957(1) Å, β = 91.29(3) °), and Ba₂P₂Se₆ (a = 10.355(2), b = 7.862(2), c = 7.046(1) Å, β = 90.83(3) °) are isotypic and crystallize in the high temperature form of Sn₂P₂S₆ (P2₁/n; Z = 2). The discrete ethanlike (P₂X₆)^4— anions in staggered conformation are linked via X—M—X bonds to a three‐dimensional structure and in the course of this Ca²⁺, Sr²⁺, and Eu²⁺ are coordinated by 8 and Ba²⁺ by 8+1 S and Se atoms respectively. Susceptibility measurements of Eu₂P₂S₆ from 2 K to room temperature show Curie‐Weiss behavior with an experimental magnetic moment of 7.43(2) μ_B/Eu. No magnetic ordering was observed down to 2 K. A ¹⁵¹Eu Mössbauer spectrum at 77 K shows only one signal at an isomer shift of δ = —12.6(1) mm/s. The europium atoms in Eu₂P₂S₆ are therefore in a stable divalent oxidation state.     

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

The complexes of 2,11‐dithia‐4,5,6,7,8,9‐hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu₂I₂(dthhpcp)₂]·2H₂O 1 , or with Ag(I), i.e. [Ag(dthhpcp)(NO₃)]thf 2 and [Ag(dthpcp)(CF₃COO)] 3 , were prepared for structural study by single‐crystal X‐ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi‐diminished structures. Complex 1 is a novel two‐dimensional coordination polymer composed of Cu₆ motifs, in which Cu₂I₂ formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three‐dimensional channel framework of silver(I) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3 , which is composed of infinite linear chains of‐Ag‐dthhpcp‐Ag‐dthhpcp‐ along the a axis. Unit cell data: complex 1 , orthorhombic system, space group P2(1)2(1)2(1), a = 19.2982(11) Å b = 16.5661(10) Å, c = 25.3006(15) Å, β = 90°, Z = 8; complex 2 , orthorhombic system, space group Pna2(1), a = 8.8595(6) Å, b = 12.6901(9) Å, c = 19.8449(14) Å, β = 90°, Z = 4; complex 3 , monoclinic system, space group P2(1)/n, a = 8.845(3) Å, b = 20.841(6) Å, c = 11.061(3) Å, β = 107.832(6)°, Z = 4.     

Synthesis and Characterization of the Rubidium Thiophosphate Rb6(PS5)(P2S10) and the Rubidium Silver Thiophosphates Rb2AgPS4, RbAg5(PS4)2 and Rb3Ag9(PS4)4

The metal thiophosphates Rb₂AgPS₄ ( 2 ), RbAg₅(PS₄)₂ ( 3 ), and Rb₃Ag₉(PS₄)₄ ( 4 ) were synthesized by stoichiometric reactions, whereas Rb₆(PS₅)(P₂S₁₀) ( 1 ) was prepared with excess amount of sulfur. The compounds crystallize as follows: 1 monoclinic, P2₁/c (no. 14), a = 17.0123(7) Å, b = 6.9102(2) Å, c = 23.179(1) Å, β = 94.399(4)°; 2 triclinic, P$\bar{1}$ (no. 2), a = 6.600(1) Å, b = 6.856(1) Å, c = 10.943(3) Å, α = 95.150(2)°, β = 107.338(2)°, γ = 111.383(2)°; 3 orthorhombic, Pbca (no. 61), a = 12.607(1) Å, b = 12.612(1) Å, c = 17.759(2) Å; 4 orthorhombic, Pbcm (no. 57), a = 6.3481(2) Å, b = 12.5782(4) Å, c = 35.975(1) Å. The crystal structures contain discrete units, chains, and 3D polyanionic frameworks composed of PS₄ tetrahedral units arranged and connected in different manner. Compounds 1 – 3 melt congruently, whereas incongruent melting behavior was observed for compound 4 . 1 – 4 are semiconductors with bandgaps between 2.3 and 2.6 eV and thermally stable up to 450 °C in an inert atmosphere.     

Structural investigation of ethylenediaminium tetrachloroaurates(III)

The (EnH₂)[AuCl₄]₂·2H₂O (I) and (EnH₂)₂[AuCl₄]Cl₃ (II) (EnH ₂ ²⁺ is diprotonated ethylenediamine) complexes are produced and characterized by elemental and thermogravimetric analysis, X-ray diffraction, IR and Raman spectroscopy. For I, the crystals are monoclinic, crystallize in the space group P2₁/c: a = 7.5870(2) Å, b = 9.5665(2) Å, c = 11.4706(3) Å, β = 107.0480(10)°, V = 795.97(3) ų, Z = 4. For II, the crystals are orthorhombic, crystallize in the space group Pnma: a = 12.7088(3) Å, b = 17.7435(5) Å, c = 7.4992(2) Å, V = 1691.06(8) ų, Z = 8.     

Two Dieneplatinum Synthetic Reagents,Pt(C6H2F3‐2,4,6)2(cod) and Pt(C6HF4‐2,3,4,5)2(cod)

Reactions of PtCl₂(cod) (cod = cycloocta‐1,5‐diene) with 2,4,6‐trifluoro‐ and 2,3,4,5‐tetrafluoro‐phenyllithium in diethyl ether gives Pt(C₆H₂F₃‐2,4,6)₂(cod) ( 1 ) (monoclinic, P2₁/n, Z = 4, a = 7.141(1), b = 15.002(2), c = 17.071(3) Å, β = 91.37(2)°) and Pt(C₆HF₄‐2,3,4,5)₂(cod) ( 2 ) (triclinic, P 1, Z = 2, a = 10.150(2), b = 10.762(2), c = 10.812(2) Å, α = 63.606(3), β = 63.327(3), γ = 76.496(3)°) respectively, which have two ipso carbon atoms and two double bond midpoint centres in a square planar arrangement, and aromatic rings angled near perpendicular to the coordination plane.     

X-ray and mössbauer studies of tricyclohexyltin(IV) halides. The crystal structures of (cyclo-C6H11)3SnX (X = F,Br and I)

The structures of tricyclohexyltin fluoride (I), bromide (II) and iodide (III) have been determined by X-ray analysis. Compound I crystallizes in the space group P2₁/m with a = 10.422(6), b = 17.238(9), c = 5.769(3) Å, β = 104.6(1)° and Z = 2. Compounds II and III crystallize in the space group Pcmn with a = 10.427(6), b = 16.914(9), c = 11.366(6) Å, Z = 4; and a = 10.400(6), b = 16.900(10), c = 11.400(4) Å, Z = 4, respectively. All three structures consist of discrete tetrahedral (cyclo-C₆H₁₁)₃SnX units.The temperature dependence of the Mössbauer resonance areas has been examined in order to obtain information about the relationship between chemical structure and lattice dynamics.     

Crystal structures of new isostructural oxovanadium(V) complexes with hydrazone ligands

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L¹)(OMe)]₂ (1) and [VO(L²)(OMe)]₂ (2), where L¹ and L² are the deprotonated forms of 3-bromo-N′-[1-(2-hydroxyphenyl)×ethylidene]benzohydrazide (H₂L¹) and 3-chloro-N′-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L²) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3)°, γ = 77.869(3)°, V = 849.9(4) ų, Z = 1, R ₁ = 0.0634, wR ₂ = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2)°, β = 71.783(2)°, γ = 79.822(2)°, V = 835.0(4) ų, Z = 1, R ₁ = 0.0511, wR ₂ = 0.1076. Each V atom in the complexes is octahedrally coordinated.     

Synthesis,Crystal Structures,and Characterization of Two 3d‐3d Heterometallic Coordination Frameworks: [ZnCo(Hcit)Cl] and [ZnCo(Hcit)Br]

Reactions between CoO, ZnCl₂ (or ZnBr₂), and molten citric acid (Hcit) led to the formation of two 3d‐3d heterometallic coordination frameworks: [ZnCo(Hcit)Cl] ( 1 ) and [ZnCo(Hcit)Br] ( 2 ). X‐ray structure analyses show that both compounds 1 and 2 crystallize in the monoclinic space group P2₁/n [ 1 : a = 5.8699(5) Å, b = 17.7963(13) Å, c = 9.2152(8) Å, β = 106.806(4) °, Z = 4, V = 921.53(13) Å³; 2 : a = 5.909(3) Å, b = 17.798(8) Å, c = 9.302(5) Å, β = 106.374(7) °, Z = 4, V = 938.6(8) Å³]. The structures of the two compounds are almost the same except for the terminal halogen ligand. Both of them are 3D frameworks based on citric acid bridging ligands and a 1D backbone chain built of corner‐shared {CoO₆} and {ZnO₃Cl} polyhedra. Photoluminescence and thermal stabilities of the compounds were studied.     

THE CRYSTAL STRUCTURES OF AMMONIUM AND SODIUM 2-AMINO-3,5-DICHLOROBENZOATES

Abstract

The crystal structures of ammonium and sodium 2-amino-3,5-dichlorobenzoates were determined by the X-ray diffraction method. The ammonium salt crystallizes in the monoclinic system (space group P2₁/c) with a = 13.941(3), b = 9.128(3), c = 7.349(2) Å, β = 90.80(3)° and Z = 4. The structure consists of an ammonium cation hydrogen bonded to a carboxylate oxygen of the 2-amino-3,5-dichlorobenzoate anion. The sodium salt of 2-amino-3,5-dichlorobenzoic acid crystallizes in the triclinic system (space group P 1) with a = 8.033(2), 6 = 8.944(2), c = 17.350(3) Å, α = 76.72(3)°, β = 79.69(3)°, γ = 72.54(3)° and Z = 4. The compound is a polymer in which the sodium ions are coordinated by carboxylate oxygen atoms of the organic ligand and water molecules in an octahedral arrangement. IR spectra of the salts are discussed.     

Structural and Kinetic Considerations for the Application of the Traceless Staudinger Ligation to Future 18F Radiolabeling Using XRD and 19F NMR

A 4‐fluorobenzoate‐functionalized phosphane was synthesized and reacted with different azides using the traceless Staudinger ligation as a representative sample reaction for future radiolabeling purposes with short‐lived radionuclides like fluorine‐18. For this purpose, the reaction rate was evaluated at different temperatures. The effect of starting material concentrations and the influence of the steric effect coming from the applied azides were investigated. ¹⁹F NMR was used to determine the reaction half‐live (τ_1/2) and the reaction rate constant (k_obs) of this ligation under mild reaction conditions in a water–acetonitrile mixture. Furthermore, the phosphane key compound 1 (orthorhombic, space group Pna2₁, a = 18.6363(9), b = 8.3589(4), c = 18.5480(9) Å, V = 2889.4(2) ų, Z = 8, D_obs = 1.277 g/cm³), which acts as starting material for all subsequent syntheses, and the fluorine‐containing phosphane 3 (monoclinic, space group P2₁/c, a = 8.321(2), b = 16.160(4), c = 14.940(4) Å, β = 99.51(1)°, V = 1981.4(8) ų, Z = 4, D_obs = 1.342 g/cm³) were analyzed by single‐crystal XRD.