Synthesis of Phosphanes Bearing 2‐Imino‐1,3‐thiazolidine Ligands – X‐Ray Analyses and NMR Spectroscopy

Pseudo‐ephedrine derived 2‐imino‐1,3‐thiazolidine 1 reacts with tris(diethylamino)phosphane by stepwise replacement of the diethylamino group to give the mono‐, bis‐ and tris(imino)phosphanes 2 , 3 and 4 , respectively, of which 4 could be isolated in pure state. The analogous reaction with diethylamino‐diphenylphosphane affords the imino‐diphenylphosphane 5 . The iminophosphanes react with sulfur or selenium to give the corresponding phosphorus(V) compounds. In contrast, the reaction of the iminophosphanes with oxygen is very slow; anhydrous trimethylamine N‐oxide reacts in the melt with the phosphanes to give the oxides 4(O) and 5(O) . The molecular structures of 4(O) (in mixture with 4 ), 4(Se) , 5(S) and 5(Se) were determined by X‐ray analysis. In all cases the ring‐sulfur and the phosphorus atoms are in cis‐positions at the C=N bonds. The analogous solution structures were determined by ¹H, ¹³C, ¹⁵N, ³¹P and ⁷⁷Se NMR spectroscopy. In the case of the compounds 5 , 5(O) , 5(S) and 5(Se) the isotope‐induced chemical shifts ¹δ^14/15N(³¹P) were determined, using INEPT‐HEED experiments.     

Mono‐ and Perfluoroaryliodine(III) Cyano Compounds – Synthesis,Reactivity, and Structure

C₆F₅I(CN)₂ and x‐FC₆H₄I(CN)₂ (x = 2, 3, 4) were isolated from reactions of the corresponding aryliodine difluorides ArIF₂ and a stoichiometric excess of Me₃SiCN in CCl₃F (0 °C) or CH₂Cl₂ (20 °C), respectively. In addition, x‐FC₆H₄I(CN)₂ compounds were synthesized in good yields on alternative routes, namely from 3‐ or 4‐FC₆H₄I(OC(O)CH₃)₂ or 4‐FC₆H₄I(OC(O)CF₃)₂ or from 4‐FC₆H₄IO and Me₃SiCN in CH₂Cl₂ at 20 °C. In the 1 : 1 reaction of C₆F₅IF₂ and Me₃SiCN a lower temperature was necessary to suppress partial disubstitution and to obtain the first example of a new type of aryliodine(III) cyanide compounds, C₆F₅I(CN)F. 4‐FC₆H₄I(CN)F could be isolated from the equimolar reaction of 4‐FC₆H₄IF₂ and Me₃SiCN in CH₂Cl₂ even at 20 °C. The new products were characterized by multi‐NMR and Raman spectroscopy. The molecular structures of C₆F₅I(CN)₂, 3‐ and 4‐FC₆H₄I(CN)₂, C₆F₅I(CN)F, and 4‐FC₆H₄I(CN)F are discussed and compared with that of C₆F₅IF₂. The reactivity of C₆F₅I(CN)F towards fluoride acceptors EF_n (BF₃, AsF₅) and R_xEX_?x (C₆F₅SiF₃, C₆H₅SiF₃, C₆H₅PF₄, Me₃SiCl, Me₃SiC₆F₅) were investigated and showed differing reaction patterns (fluoride abstraction, aryl transfer, chloride transfer). Besides the molecular entities C₆F₅I(CN)F and C₆F₅I(CN)Cl, the corresponding iodonium salts [C₆F₅(CN)I][BF₄] and [C₆F₅(CN)I][AsF₆] were isolated. The thermal stability of ArI(CN)₂ and ArI(CN)F, neat and in solution, as well as the reactivity of 4‐FC₆H₄I(CN)₂ towards the Lewis acid BF₃ are reported.     

An Alternative Method for the Preparation of Diphenylboron Chelates. The Crystal and Molecular Structures of (Pyridine‐2‐acetyloximato)diphenylboron and (1‐Phenylazo‐2‐naphtholato)diphenylboron

A convenient method for the preparation of diphenylboron chelates from ammonium tetraphenylborate is described. A variety of five‐ or six‐membered O,O‐, N,O‐ and N,N‐chelates were obtained in yields from 60 to 90 %. The isolated compounds were characterized by elemental analysis, IR spectroscopy and multinuclear magnetic resonance spectroscopy (¹H, ¹³C, and ¹¹B). The crystal and molecular structures of (pyridine‐2‐acetyloximato)diphenylboron and (1‐phenylazo‐2‐naphtholato)diphenylboron were determined by X‐ray diffraction on single crystals.     

Structural and NMR Studies of the Hexameric Copper(I) Complex with N‐n‐butyl‐N′‐ethoxycarbonyl‐thioureate

The copper sulfide mineral flotation collector, N‐n‐butyl‐N′‐ethoxycarbonyl‐thiourea (H₂bectu), and the 1:1 hexameric copper(I) thioureate complex, [Cu(Hbectu)]₆, have been characterized by single crystal X‐ray diffraction. H₂bectu crystallizes in the triclinic space group with a = 5.2754(4), b = 9.0042(7), c = 12.6030(9) Å, α = 80.528(6), β = 90.173(6), γ = 76.472(7)°. An intramolecular N‐H···O hydrogen bond between the thioamide proton and carbonyl oxygen forms a planar six‐membered ring in the central core of the molecule with C=O, C=S and C‐N bond lengths in accord with those reported for other N‐alkyl/aryl‐N′‐acyl‐thiourea compounds. [Cu(Hbectu)]₆ crystallizes in the monoclinic space group C2/c with a = 23.269(5), b = 13.243(4), c = 23.037(7) Å, β = 91.81(2)° as discrete hexameric clusters disposed about a crystallographic centre of symmetry with a Cu₆S₆ core consisting of two Cu₃S₃ chair‐shaped rings linked by coordination of the deprotonated amide nitrogen atom to a copper atom in the adjacent ring. The six ligands assemble as a paddlewheel structure with the ethoxy and n‐butyl substituents packing in an alternating head to tail arrangement. Temperature dependent solution ¹H NMR spectroscopic studies show that the hexameric structure of the complex is maintained in solution.     

Synthesis and Characterization of 3,4,5‐Triamino‐1,2,4‐triazolium and 1‐Methyl‐3,4,5‐triamino‐1,2,4‐triazolium Iodides

3,4,5‐Triamino‐1,2,4‐triazolium iodide ( 1 ) was obtained in good yield and purity and characterized using vibrational (IR, Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N), EA, MS, DSC, and X‐ray crystallography. The compound was synthesized by two different methods rendering two different polymorphs (α and β) as proved by X‐ray measurements, vibrational spectroscopy and DSC. 1‐Methyl‐3,4,5‐triamino‐1,2,4‐triazolium iodide ( 2 ) was synthesized by reaction of guanazine with methyliodide and fully characterized by the same techniques mentioned above. Both compounds showed to be suitable starting materials for the synthesis of guanazinium salts of energetic interest.     

Synthesis,Structure and Selective Chlorination of Bis(N‐borane‐dimethylaminopropyl)telluride

The reaction of Te powder, NaBH₄ and Me₂N(CH₂)₃Cl·HCl provided the title compound [H₃BNMe₂(CH₂)₃]₂Te ( 1 ), whose selective chlorination with SO₂Cl₂ lead to the formation of [ClH₂BNMe₂(CH₂)₃]₂TeCl₂ ( 2 ) and [Cl₃BNMe₂(CH₂)₃]₂TeCl₂ ( 3 ), respectively. Compounds 1 – 3 were characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction.     

Synthesis and Structural Characterization of Some Novel Trialkylsilyl‐substituted Lithium Benzyl Complexes [Li(tmeda)][CHRSiMe2R′] (R = Ph, 3,5‐Me2C6H3; R′ = Me,tBu, Ph)

The reactions of PhCH₂SiMe₃ ( 1 ), PhCH₂SiMe₂^tBu ( 2 ), PhCH₂SiMe₂Ph ( 3 ), 3,5‐Me₂C₆H₃CH₂SiMe₃ ( 4 ), and 3,5‐Me₂C₆H₃CH₂SiMe₂^tBu ( 5 ) with ⁿBuLi in tetramethylethylenediamine (tmeda) afford the corresponding lithium complexes [Li(tmeda)][CHRSiMe₂R′] (R, R′ = Ph, Me ( 6 ), Ph, ^tBu ( 7 ), Ph, Ph ( 8 ), 3,5‐Me₂C₆H₃, Me ( 9 ), and 3,5‐Me₂C₆H₃, ^tBu ( 10 )), respectively. The new compounds 5 , 7 , 8 , 9 and 10 have been characterized by ¹H and ¹³C NMR spectroscopy, compounds 7 , 8 and 9 also by X‐ray structure analysis.     

Synthesis,Crystal Structure and Spectroscopic Properties of Bis(1‐(E)‐2‐formylpyridine semicarbazone)nickel(II) Diperchlorate Monohydrate

Pale‐green crystals of the title complex were prepared by reaction of 2‐formylpyridine semicarbazone (HCSpy) and nickel(II) perchlorate in boiling ethanol. The crystals are triclinic with the nickel ion in an octahedral arrangement, coordinated by two nitrogen atoms and one oxygen donor atom from each ligand molecule. The effect of coordination on bond lengths and angles was explored by comparison with the single‐crystal structure data of the free ligand HSCpy, which was collected as well. The assumed coordination mode was supported by ¹H and ¹³C NMR spectroscopic data. A detailed analysis of the electronic properties, including semi‐empirical quantummechanical calculations is presented. Furthermore, the data obtained from magnetic susceptibility and EPR measurements are in accordance with a low‐spin d⁸ nickel(II) complex.     

Synthese,Strukturen, NMR‐ und EPR‐spektroskopische Untersuchungen an Übergangsmetallkomplexen monofluorsubstituierter Acylselenoharnstoffliganden

Synthesis, Structures, NMR and EPR Investigations on Transition Metal Complexes of monofluorosubstituted Acylselenourea Ligands The syntheses and the structures of the ligand N, N‐diethyl‐N′‐(2‐fluoro)benzoylselenourea HEt₂mfbsu and the complexes [Ni(Et₂mfbsu)₂] and [Zn(Et₂mfbsu)₂] as well as of the ligand N, N‐diisobutyl‐N′‐(2‐fluoro)benzoylselenourea HBuⁱ₂mfbsu and the complexes [Ni^II(Buⁱ₂mfbsu)₂] and [Pd^II(Buⁱ₂mfbsu)₂] are reported. The ligands coordinate bidendately forming bischelates. The Pd^II and Ni^II complexes are cis coordinated; in [Zn^II(Et₂mfbsu)₂] the ligands are tetrahedrally arranged. The structure of the also obtained bis[diisobutylamino‐(2‐fluorobenzoylimino)methyl]diselenide is reported. The Cu^II complexes of both selenourea ligands could not be isolated. They were obtained as oils. Their EPR spectra, however, confirm the presence of Cu^II bischelates unambiguously. Detailed NMR investigations ‐ ¹H‐, ¹³C‐ and ¹⁹F‐COSY, HMBC and HMQC ‐ on [M^II(Et₂mfbsu)₂] (M = Ni^II, Zn^II) allow an exact assignment of all signals to the magnetically active nuclei of the complexes.     

Hydroaluminierung: Synthese,Struktur und Eigenschaften von 1‐Methyl‐cis‐1‐azonia‐5‐alabicyclo[3.3.0]octan und des Alan‐triallylamin‐Adduktes

Hydro‐Alumination: Synthesis, Structure, and Properties of 1‐Methyl‐ cis ‐1‐azonia‐5‐alabicyclo[3.3.0]octane and of the Alan‐triallylamine Adduct The alan‐N‐methyl‐diallylamine adduct ( I ) was obtained by the reaction of N,N‐diallyl‐methyl‐ammoniumchloride with LiAlH₄. Subsequently the reaction product was transformed by intramolecular hydro‐alumination reaction into bis(1‐methyl‐cis‐1‐azonia‐5‐alabicyclo[3.3.0]octane) ( II ). In contrast to I , the bis(alan‐triallylamine) adduct ( III ) does not undergo an analogous hydro‐alumination reaction. The compounds I , II and III were characterized by MS, IR, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and the X‐ray structures of II and III are reported and discussed.     

Synthese,Strukturen, NMR‐ und EPR‐Untersuchungen der binuklearen Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenoureato))‐Komplexe des NiII und CuII

Synthesis, Structures, NMR and EPR Investigations of Binuclear Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenoureato)) Complexes of Ni^II and Cu^II The synthesis of binuclear Cu^II and Ni^II complexes of the quadridentate ligand N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenourea) and their crystal structures are reported. The complexes crystallize monoclinic, P2₁/c (Z = 2). In the EPR spectra of the binuclear Cu^II complex exchange‐coupled Cu^II‐Cu^II pairs were observed. In addition the signals of a mononuclear Cu^II species are observed what will be explained with the assumption of an equilibrium between the binuclear Cu^II‐complex (Cu^II‐Cu^II pairs) and oligomeric complexes with “isolated” Cu^II ions. Detailed ¹³C and ⁷⁷Se NMR investigations on the ligand and the Ni^II complex allow an exact assignment of all signals of the heteroatoms.     

Dimethylerdmetall‐Heterocyclen als Derivate trimethylsilylierter, ‐germylierter und ‐stannylierter Phosphane und Arsane – Synthesen,Spektren und Strukturen

Dimethyl Earth‐Metal Heterocycles – Derivatives of Trimethyl‐silylated, ‐germylated, and ‐stannylated Phosphanes and Arsanes – Syntheses, Spectra, and Structures The organo earth‐metal heterocycles [Me₂M^III–E(M^IVMe₃)₂]_n with M^III = Al, Ga, In; E = P, As; M^IV = Si, Ge, Sn and n = 2, 3 (Me = CH₃) have been prepared from the dimethyl metal compounds Me₂M^IIIX (X = Me, H, Cl, OMe, OPh) and the pnicogen derivatives H_nE(M^IVMe₃)_3–n (n = 0, 1) according to known preparation methods. The mass, ¹H, ¹³C, ³¹P, ²⁹Si, ¹¹⁹Sn nmr, as well as the ir and Raman spectra have been discussed comparatively; selected representatives are characterized by X‐ray structure analyses. The dimeric species with four‐membered (E–M^III)₂ rings are isotypic and crystallize in the triclinic space group P1, the trimer [Me₂In–P(SnMe₃)₂]₃ with a strongly puckered (In–P)₃‐ring skeleton crystallizes with two formula units per cell in the same centrosymmetric triclinic space group.     

Synthesis and Spectroscopic Study of Some New Phosphoramidates,Crystal Structures of N‐Benzoyl‐N′,N″‐bis(azetidinyl)phosphoric Triamide and N‐Benzoyl‐N′,N″‐bis(hexamethylenyl)phosphoric Triamide

Some new N‐carbonyl, phosphoramidates with formula C₆H₅C(O)N(H)P(O)R₂ (R = NC₃H₆ ( 1 ), NC₆H₁₂ ( 2 ), NHCH₂CH=CH₂ ( 3 ), N(C₃H₇)₂ ( 4 )) and CCl₃C(O)N(H)P(O)R′₂ (R′ = NC₃H₆ ( 5 ), NHCH₂CH=CH₂ ( 6 )) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR and IR spectroscopy and elemental analysis. The structures were determined for compounds 1 and 2 . Compound 1 exists as two crystallographically independent molecules in crystal lattice. Both compounds 1 and 2 produced dimeric aggregates via intermolecular ‐P=O…H‐N‐ hydrogen bonds, which in compound 2 is a centrosymmetric dimer. In compounds with four‐membered ring amine groups, ³J(P,C)>²J(P,C), in agreement with our previous studies about five‐membered ring amine groups. Also, ³J(P,C) values in compounds 1 and 5 are greater than in compounds with five‐, six‐ and seven‐membered ring amine groups.     

Ferrocenophanes with Interannular Nitrogen–Gallium Bridges. 1,3,2‐Diazagalla‐[3]Ferrocenophanes and an 1‐Aza‐3‐Azonia‐2‐Gallata‐[3]Ferrocenophane. Synthesis and Structure

1,1′‐Bis(trimethylsilylamino)ferrocene reacts with trimethyl‐ and triethylgallium to give the μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetraalkyldigallanes. These were converted into the 1,3‐bis(trimethylsilyl)‐2‐alkyl‐2‐pyridine‐1,3,2‐diazagalla‐[3]ferrocenophanes, of which the ethyl derivative was characterized by X‐ray structural analysis. Treatment of gallium trichloride with N,N′‐dilithio‐1,1′‐bis(trimethylsilylamino)ferrocene affords μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetrachlorodigallane along with bis(trimethylsilyl)‐2,2‐dichloro‐1‐aza‐3‐azonia‐2‐gallata‐[3]ferrocenophane as a side product, and both were structurally characterized by X‐ray analysis. The solution‐state structures of the new gallium compounds and aspects of their molecular dynamics in solution were studied by NMR spectroscopy (¹H, ¹³C, ²⁹Si NMR).     

Synthesis,Characterization, and Crystal Structure of 1,3‐Dipentafluorophenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine

1,3‐Dipentafluorophenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine ( 1 ) was synthesized by the reaction of [(C₆F₅)NPCl₃]₂ with trimethylsilyl azide in CH₂Cl₂ and characterized by multinuclear NMR and vibrational spectroscopy. The molecular structure of the compound was determined by single‐crystal X‐ray structure analysis. [(C₆F₅)NP(N₃)₃]₂ crystallizes in the monoclinic space group P2₁/n with a = 9.6414(2), b = 7.4170(1) and c = 15.9447(4) Å, β = 94.4374(9)°, with 2 formula units per unit cell. The bond situation in [(C₆F₅)NP(N₃)₃]₂ has been studied on the basis of NBO analysis. The antisymmetric stretching vibration of the azide groups is discussed. The structural diversity of 1 and 1,3‐diphenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine in solution and in the solid state depending on the aryl substituent at the nitrogen atom is discussed.     

Synthesis,Structure, Chemical and Energetic Characterization of 1,3‐Dinitramino‐2‐nitroxy‐propane

The title compound, 1,3‐dinitramino‐2‐nitroxy‐propane ( 1 ) was prepared in high yield (85 %) and characterized by multinuclear NMR (¹H, ¹³C, ¹⁴N) and vibrational (IR, Raman) spectroscopy. The molecular structure in the solid state was elucidated by single crystal X‐ray diffraction. 1 crystallizes in the orthorhombic space group P_nma with a crystal density of ρ = 1.798 g cm^?3. Compound 1 melts at 166 °C and decomposes at 168 °C. The impact (7 J), friction (96 N) and electrostatic discharge sensitivities (0.6 J) were determined experimentally. The detonation parameters of 1 were calculated using a combined quantum chemical (CBS‐4M) calculation and a chemical equilibrium calculation based on the steady‐state model of detonation: Q = ?5998 kJ kg^?1, P = 339 kbar, D = 8895 m s^?1. The experimentally determined detonation velocity (fiber optic method) agrees well with the calculated values. In comparison with picric acid (PA) and nitropenta (PETN), compound 1 shows superior detonation characteristics when detonated in a confined space.     

Structures and Spectroscopy of some Adducts of Coinage Metal(I) Cyanides with ‘Tetrahedral’‐Unidentate‐N‐Bases

Crystallization of copper(I) cyanide from piperidine (‘pip’) solution yields an adduct of CuCN : pip (3 : 4) ratio, as established by a single crystal X‐ray structure determination, which also shows the complex to have a single‐stranded ···Cu(CN)Cu(CN)···spine (C,N scrambled), one‐third of the copper atoms carrying a pair of pip ligands, the others only one. Crystallization of silver(I) cyanide from piperidine (‘pip’) or cyclohexylamine (‘CyNH₂’) solutions yields adducts of the unusual AgX : unidentate‐N‐base (1 : 2) stoichiometry. The CyNH₂ adduct is, unusually for cyanide complexes of this type, mononuclear with a trigonal planar silver atom, [(NC)Ag(H₂NCy)₂], the AgCN component lying along the intersection of two crystallographic mirror planes which bisect and relate the H₂NCy ligands (Ag‐C, N 2.067(3), 2.335(2) Å; N‐Ag‐N, C 80·80(6), 139.60(4)°). In the pip adduct, the immediate silver atom environment is also three‐coordinate (Ag‐C; N, N 2.080(1); 2.288, 2.443(1) Å; N‐Ag‐N 88·34(4), N‐Ag‐C 144.47(4), 125.07(4), (Σ357.₉°) perturbed toward two‐coordination, but the silver atom environment geometry is further perturbed from planarity by the parallel approach of an inversion‐related molecule (Ag···C′ 2.926(1) Å (Ag···Ag′ 3.1842(2)°) forming a loose, albeit still discrete, dimer. Key features in the IR spectra of the above compounds and of AgCN : pip (1 : 1) and CuCN : CyNH₂ (2 : 3) are assigned and discussed in terms of the structures or of proposed structures in the case of the latter two adducts. The structure of [ClAg(pip)₃], adventitiously obtained, is also described (Ag‐Cl 2.471(3); Ag‐N 2.147(13), 2.188(7) (x2) Å; Cl‐Ag‐N 96.1(3), 98.5(2), N‐Ag‐N 116.3(2) (x2), 122.1(3)°).     

(Carb)2SnF4 (Carb = 2, 3‐Dihydro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazol‐2‐yliden – ein Carbenkomplex des vierwertigen Zinns

2, 3‐Dihydro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazol‐2‐ylidene ( 1 , Carb) reacts with tin tetrafluoride to give the complex (Carb)₂SnF₄ ( 3 ). The ligand properties of 1 are discussed in terms of the crystal structure and NMR data of 3 .     

Synthesis,Characterization and Crystal Structure of 4‐Amino‐1,2,4‐Δ2‐triazoline‐5‐thione and its Silver(I) Complex

The reaction of 4‐amino‐1,2,4‐Δ²‐triazoline‐5‐thione (ATT, 1 ) with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, ¹H NMR, IR, and Raman spectroscopy as well as single‐crystal X‐ray diffraction. The molecular structure of 1 was also determined by single crystal X‐ray analysis. Crystal data for 1 at ?80 C: space group C2/c with a = 2107.4(2), b = 1425.1(1), c = 688.4(1) pm, β = 104.55(1)°, Z = 16, R₁ = 0.0514, crystal data for 2 at ?80 °C: space group P2₁/c with a = 675.7(1), b = 1321.1(1), c = 1311.2(1) pm, β = 90.03(1)°, Z = 4, R₁ = 0.0437.