Synthese und Kristallstrukturen von monomeren bis(thiophenolato)metall(II)-Komplexen

Preparation and Structures of Monomeric Bis(thiophenolato)metal(II) Complexes Sodium-2,4,6-tris(trifluoromethyl)thiophenolate (NaSR_f) reacts with MCl₂ (M = Zn, Pb) in the molar ratio of 2:1 to form the bis(thiophenolato)metal(II)complexes bis[2,4,6-tris(trifluoromethyl)thiophenolato]zinc 1 and bis[2,4,6-tris(trifluoromethyl)thiophenolato]lead 2 . Reaction of Mn[N(SiMe₃)₂]₂· THF with two equivalents of 2,4,6-tris(trifluoromethyl)thiophenol (R_fSH) forms Mn(SR_f)₂ · THF 3 . All compounds crystallize as THF adducts. The structures of Zn(SR_f)₂ · 2THF 1a , Pb(SR_f)₂ · THF 2a and Mn(SR_f)₂ · 2THF 3a are discussed.     

Synthesis,Structure, and Lanthanide Derivatives of an Unusual Hexameric Alcohol: [2,4,6-(CF3)3C6H2CH2OH]6

Hitherto unknown 2,4,6-tris(trifluoromethyl)benzyl alcohol ( 3 ) was synthesized in 41 % yield by treatment of freshly prepared R_FLi ( 2 ) with paraformaldehyde (R_F = 2,4,6-tris(trifluoromethyl)phenyl). According to an X-ray diffraction study the crystal structure of 3 consists of S₆ symmetric cyclic hexamers [2,4,6-(CF₃)₃C₆H₂CH₂OH]₆. Deprotonation of 3 with NaN(SiMe₃)₂ in toluene afforded the unsolvated sodium alkoxide derivative R_FCH₂ONa ( 4 ). Homoleptic lanthanide alkoxides of the type Ln(OCH₂R_F)₃ (Ln = Nd ( 5 ), Sm ( 6 ), Yb ( 7 )) were made by treatment of Ln(C₅H₅)₃ with three equivalents of 3 . Similar reactions in a 1:1 molar ratio afforded the bis(cyclopentadienyl)lanthanide alkoxide derivatives (C₅H₅)₂Ln(OCH₂R_F) (Ln = Nd ( 8 ), Sm ( 9 ), Yb ( 10 )).     

Erste Kristallstruktur eines Selenans; Metall(II)-Komplexe mit dem 2,4,6-Tris(trifluormethyl)selenophenolat-Liganden

The First Structure of a Selenane; Metal(II) Complexes with the 2,4,6-Tris(trifluoromethyl)-selenophenolato Ligand R_fSeH 1 is obtained in a single pot reaction of R_fLi [R_f = 2,4,6-tris(trifluoromethyl)phenyl] with elemental selenium and following treatment with HBF₄. 1 gave the first crystal structure of a selenane. Reaction of 1 with M[N(SiMe₃)₂]₂ (M = Zn, Pb) in the molar ratio of 2:1 yielded the metal selenophenolates Zn(SeR_f)₂ · HN(SiMe₃)₂ 2 and [Pb(SeR_f)₂]₂ 3. 2 crystallizes as hexamethyldisilazane adduct, 3 as a dimer.     

Arylvanadin(III)-Verbindungen,III. Darstellung und Eigenschaften von Triarylvanadin-Verbindungen

Arylvanadium(III) Compounds. III. Preparation and Properties of Triaryl Vanadium Complexes The synthesis of triarylvanadium compounds, VR₃ (R = C₆H₅; 2,6-(CH₃)₂C₆H₃; 2,4,6-(CH₃)₃C₆H₂; (CH₃)₅C₆) is investigated. Only the compounds V[2,6-(CH₃)₂C₆H₃]₃ and V[2,4,6-(CH₃)₃C₆H₂]₃ (crystallized with tetrahydrofuran) are obtained. The complexes V(C₆H₅)(dipy)₂ · THF, V[2,4,6-(CH₃)₃C₆H₂]₃ · Do (Do = py, dipy) are described too.     

4‐Styrylquinolines from cyclocondensation reactions between (2‐aminophenyl)chalcones and 1,3‐diketones: crystal structures and regiochemistry

Structures are reported for two matched sets of substituted 4‐styrylquinolines which were prepared by the formation of the heterocyclic ring in cyclocondensation reactions between 1‐(2‐aminophenyl)‐3‐arylprop‐2‐en‐1‐ones with 1,3‐dicarbonyl compounds. (E)‐3‐Acetyl‐4‐[2‐(4‐methoxyphenyl)ethenyl]‐2‐methylquinoline, C₂₁H₁₉NO₂, (I), (E)‐3‐acetyl‐4‐[2‐(4‐bromophenyl)ethenyl]‐2‐methylquinoline, C₂₀H₁₆BrNO, (II), and (E)‐3‐acetyl‐2‐methyl‐4‐{2‐[4‐(trifluoromethyl)phenyl]ethenyl}quinoline, C₂₁H₁₆F₃NO, (III), are isomorphous and in each structure the molecules are linked by a single C—H…O hydrogen bond to form C(6) chains. In (I), but not in (II) or (III), this is augmented by a C—H…π(arene) hydrogen bond to form a chain of rings; hence, (I)–(III) are not strictly isostructural. By contrast with (I)–(III), no two of ethyl (E)‐4‐[2‐(4‐methoxyphenyl)ethenyl]‐2‐methylquinoline‐3‐carboxylate, C₂₂H₂₁NO₃, (IV), ethyl (E)‐4‐[2‐(4‐bromophenyl)ethenyl]‐2‐methylquinoline‐3‐carboxylate, C₂₁H₁₈BrNO₂, (V), and ethyl (E)‐2‐methyl‐4‐{2‐[4‐(trifluoromethyl)phenyl]ethenyl}quinoline‐3‐carboxylate, C₂₂H₁₈F₃NO₂, (VI), are isomorphous. The molecules of (IV) are linked by a single C—H…O hydrogen bond to form C(13) chains, but cyclic centrosymmetric dimers are formed in both (V) and (VI). The dimer in (V) contains a C—H…π(pyridyl) hydrogen bond, while that in (VI) contains two independent C—H…O hydrogen bonds. Comparisons are made with some related structures, and both the regiochemistry and the mechanism of the heterocyclic ring formation are discussed.     

Synthese,Strukturen und Reaktivität von [(2,4,6-Ph3C6H2)Te(μ2-O)X]2 (X  Br und I)

Synthesis, Structures, and Reactivity of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)X]₂ (X ? Br, I) [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with iodine affording the aryltellurenic halide (2,4,6-Ph₃C₆H₂)TeI, which is oxidized by oxygen to yield [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂. It crystallizes with two molecules of dichloromethane in the monoclinic space group P2₁/c with a unit cell of the dimensions a = 911.3(4); b = 1153.3(2); c = 2244.1(9) pm; β = 93.53(2)°, Z = 2). The analogues bromo compound [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)Br]₂ is obtained by the reaction of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ with NH₄Br. It crystallizes with two molecules of xylene in the monoclinic space group P2₁/n (a = 1067.5(5); b = 1018.4(4); c = 2486.5(8) pm; β = 101.71(2)°; Z = 2). Both compounds are built up by two (2,4,6-Ph₃C₆H₂)TeX units (X ? Br, I) which are linked by two oxgen bridges to form centrosymmetric molecules. The Te? O? Te angles are 102°. Distinct Te? O bond lengths have been found (191.4(2) and 208.6(2) pm in [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ and 189.8(4)/208.4(5 pm in the bromo compound).     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Fluoroborates by Cleavage of Trimethylamine‐bis(trifluoromethyl)boranes with NEt3 × 3 HF. Structures of C6F5(CF3)2B · NMe3, K[C6H5CH2(CF3)2BF], and K[C6H5(CF3)2BF]

Trimethylamine‐bis(trifluoromethyl)boranes R(CF₃)₂B · NMe₃ (R = cis/trans‐CF₃CF=CF ( 1/2 ), HC≡C ( 3 ), H₂C=CH ( 4 ), C₂H₅ ( 5 ), C₆H₅CH₂ ( 6 ), C₆F₅ ( 7 ), C₆H₅ ( 8 )) react with NEt₃ × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF₃)₂BF]^– ( 1 a/2 a – 8 a ). The structures of 7 , K[C₆H₅CH₂(CF₃)₂BF] ( K‐6 a ), and K[C₆H₅(CF₃)₂BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF₃ groups make short repulsive contacts with NMe₃ and C₆F₅ entities – the B–CF₃ bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.     

Tri(1-cyclohepta-2,4,6-trienyl)phosphan,P(C7H7)3 und Tetra(1-cyclohepta-2,4,6-trienyl)phosphonium-tetrafluoroborat, [P(C7H7)4]BF4

Tri(1-cyclohepta-2,4,6-trienyl)phosphane, P(C₇H₇)₃, and Tetra(1-cyclohepta-2,4,6-trienyl)phosphonium Tetrafluoroborate, [P(C₇H₇)₄]BF₄ The reaction of tris(trimethylsilyl)phosphane, P(SiMe₃)₃, with tropylium bromide, C₇H₇⁺Br^?, in polar solvents such as dichloromethane or tetrahydrofuran gives P(C₇H₇)₃ ( 1 ) and [P(C₇H₇)₄]Br ( 2a ). According to the X-ray crystallographic structure determinations, all 1-cyclohepta-2,4,6-trienyl substituents are present in the boat conformation in both P(C₇H₇)₃ ( 1 ) and the phosphonium salt, [P(C₇H₇)₄]BF₄ ( 2b ). The boat-shaped C₇H₇ rings are significantly more flattened if the phosphorus occupies the axial rather than the equatorial position at the ring substituent. Addition of a chalcogen to the lone pair at the central phosphorus atom of 1 leads to the chalcogena-phosphoranes EP(C₇H₇)₃ (E = O ( 3a ), S ( 3b ), Se ( 3c )). The new 1-cyclohepta-2,4,6-trienyl-phosphorus compounds 1, 2 b and 3a–c were characterized by their ¹H, ¹³C, and ³¹P NMR spectra in C₆D₆ solution.     

A Convenient,Selective Synthesis of Bis[2,4‐bis(trifluoromethyl)phenyl]phosphane Derivatives Starting from 1,3‐Bis(trifluoromethyl)benzene

The reaction of the sterically shielded phosphane derivative, dichlorodiethylaminophosphane, Cl₂PNEt₂, with an excess of a mixture of 2,6‐bis(trifluoromethyl) and 2,4‐bis(trifluoromethyl)phenyl lithium gives bis[2,4‐bis(trifluoromethyl)phenyl]diethylaminophosphane, [2,4‐(CF₃)₂C₆H₃]₂PNEt₂, in 72 % yield as a colourless solid, while 2,6‐bis(trifluoromethyl)phenyl lithium remains unchanged in solution. The amino derivative crystallizes in the monoclinic space group P2₁/c (a 869.2(1), b 1857.4(1), c 1357.6(1) pm, β 100.57(4)°, Z = 4). Treatment of [2,4‐(CF₃)₂C₆H₃]₂PNEt₂ in CHCl₃ solution with conc. HCl allows the synthesis of [2,4‐(CF₃)₂C₆H₃)]₂PCl. [2,4‐(CF₃)₂C₆H₃]₂PCl reacts with H₂O in THF solution with quantitative formation of the corresponding secondary phosphane oxide. To obtain bis[2,4‐bis(trifluoromethyl)phenyl]phosphinic acid, [2,4‐(CF₃)₂C₆H₃]₂P(O)OH, quantitatively, a CHCl₃ solution of [2,4‐(CF₃)₂C₆H₃]₂P(O)H, has to be stirred in an NO₂ atmosphere. The phosphinic acid crystallizes is the triclinic space group (a 754.2(1), b 927.6(2), c 1305.5(2) pm, α 85.11(2)°, β 75.45(1)°, γ 79.99(2)°, Z = 2). From the reaction of the phosphinic acid with either elemental sodium or with cyanide salts, the corresponding phosphinate salts are obtained in an almost quantitatively yield.     

Cycloadditionsreaktionen von Trifluormethylisocyanid an Diphosphene. Synthese und Struktur des neuartigen 2-Phosphiniden-1, 3-azaphospholidins

Cycloaddition Reactions of Trifluoromethyl Isocyanide with Diphosphenes. Synthesis and Structure of the new 2-Phosphinidene-1,3-azaphospholidine Derivative [2 + 1] Cycloaddition reactions of trifluoromethyl isocyanide 1 and methylisocyanide 2 with the diphosphene R? P?P? R 3a ( a R ? C[Si(CH₃)₃]₃) yield the three membered heterocyclic diphosphirane imines 4 and 5 , respectively. Whereas the trifluoromethyl substituted compound 4 is thermally very stable, the methylsubstitued derivative 5 slowly looses methyl isocyanide reforming the diphosphene 3a . In the reaction of 1 with R? P?P? R 3b [ b R = 2,4,6-(t-Bu)₃C₆H₂] no evidence for the formation of a three membered ring compound could be obtained. The five membered heterocycle 3-(2,4,6-Tri-t-butylphenyl)-2-[2,4,6-tri-t-butylphenyl)-phosphinidene]-1-trifluoromethyl-4, 5-bis(trifluoromethylimin)-1,3-azaphospholidine 6 was isolated as the only product together with unreacted 3b . The structure of 6 , triclinic, P1 , a = 1081.1(8), b = 1463.1(11), c = 1643.6(5)pm, α = 64.01(6), β = 81.22(4), γ = 74.04(5)°, Z = 2, R = 0.080, R_w = 0.085, has been elucidated by X-ray diffraction.     

Basische metalle: LII. Synthese von carbenoid- und ylidcobalt(III)-komplexen aus substitutionslabilen cobalt(I)-vorstufen

The cyclopentadienylcobalt(I) compounds C₅H₅Co(PMe₃)P(OR)₃ (R = Me, Et, Prⁱ) and C₅H₅Co(C₂H₄)L (L = PMe₃, P(OMe)₃, CO) are prepared by ligand substitution starting from C₅H₅Co(PMe₃)₂ and C₅H₅Co(C₂H₄)₂. Whereas the reaction of C₅H₅Co(PMe₃)P(OMe)₃ with CH₂Br₂ mainly gives [C₅H₅CoBr(PMe₃)P(OMe)₃]Br, the dihalogenocobalt(III) complexes C₅H₅CoX₂(PMe₃) (X = Br, I) are obtained from C₅H₅Co(CO)PMe₃ and CH₂X₂. Treatment of C₅H₅Co(CO)PMe₃ or C₅H₅Co(C₂H₄)PMe₃ with CH₂ClI at low temperatures produces a mixture of C₅H₅CoCH₂Cl(PMe₃)I and C₅H₅CoCl(PMe₃)I, which can be separated due to their different solubilities. The same reaction in the presence of ligand L gives the carbenoidcobalt(III) compounds [C₅H₅CoCH₂Cl(PMe₃)L]PF₆ in nearly quantitative yields. If NEt₃ is used as the Lewis base, the ylide complexes [C₅H₅Co(CH₂PMe₃)(PMe₃)X]PF₆ (X = Br, I) are obtained. The PF₆ salts of the dications [C₅H₅Co(CH₂PMe₃)(PMe₃)L]²⁺ (L = PMe₃, P(OMe)₃, CNMe) and [C₅H₅Co(CH₂PMe₃)(P(OMe)₃)₂]²⁺ are prepared either from [C₅H₅Co(CH₂PMe₃)(PMe₃)X]⁺ and L, or more directly from C₅H₅Co(CO)PMe₃, CH₂X₂ and PMe₃ or P(OMe)₃, respectively. The synthesis of C₅H₅CoCH₂OMe(PMe₃)I is also described.     

Unerwartete Reduktion von [Cp*TaCl4(PH2R)] (R = But,Cy, Ad,Ph, 2,4,6‐Me3C6H2; Cp* = C5Me5) durch Reaktion mit DBU – Molekülstruktur von [(DBU)H][Cp*TaCl4] (DBU = 1,8‐Diazabicyclo[5.4.0]undec‐7‐en)

Unexpected Reduction of [Cp*TaCl₄(PH₂R)] (R = Bu^t, Cy, Ad, Ph, 2,4,6‐Me₃C₆H₂; Cp* = C₅Me₅) by Reaction with DBU – Molecular Structure of [(DBU)H][Cp*TaCl₄] (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) [Cp*TaCl₄(PH₂R)] (R = Bu^t, Cy, Ad, Ph, 2,4,6‐Me₃C₆H₂ (Mes); Cp* = C₅Me₅) react with DBU in an internal redox reaction with formation of [(DBU)H][Cp*TaCl₄] ( 1 ) (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) and the corresponding diphosphane (P₂H₂R₂) or decomposition products thereof. 1 was characterised spectroscopically and by crystal structure determination. In the solid state, hydrogen bonding between the (DBU)H cation and one chloro ligand of the anion is observed.     

Strukturen von Bis(trifluormethyl)halogeno‐ und ‐thiocyanato‐mercuraten, [Hg(CF3)2X]— (X = Br,I, SCN), und ein Vergleich der Strukturparameter der CF3‐Gruppen

Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF₃)₂X]^— (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF₃ Groups [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂X]₂ (X = Br (2) , I (3) ) are prepared and their crystal structures are determined. [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) crystallizes in the monoclinic space group P2₁/c with Z = 2, [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂Br]₂ (2) in the monoclinic space group P2₁/n with Z = 2 and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂I]₂ (3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg₂X₂ rings. The structural parameters of the Hg(CF₃)₂ units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF₃ group exist. The largest differences of the C—F bond lengths is found for [(18‐C‐6)K][Hg(CF₃)₂I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides.     

Two- and Three-dimensional Frameworks with (6,3) and (10,3)-a Topology from Self-assembly of Three-connecting Organic Ligands with Cadmium(II) and Silver(I) Salts

Assembly of three-connecting ligands 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) with cadmium(II) and silver(I) salts provide new metal-organic frameworks, [Cd(tib)₂](NO₃)₂·4H₂O (1), [Ag(tib)(PPh₃)](CF₃SO₃) (2) and [Ag(titmb)(PPh₃)](CF₃SO₃)·1.5H₂O (3) (PPh₃=triphenylphosphine). Single-crystal X-ray diffraction studies reveal that complexes 1 and 3 are two-dimensional honeycomb networks, while complex 2 is a noninterpenetrated three-dimensional architecture with (10,3)-a topology. The results indicate that the nature (structure and flexibility) of the organic ligands and the bulky auxiliary ligand have great impact on the assembly and structure of metal-organic frameworks. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature.     

Insight into the structures of [M(C5H4I)(CO)3] and [M2(C12H8)(CO)6] (M = Mn and Re) containing strong I...O and π(CO)–π(CO) interactions

The compounds tricarbonyl(η⁵‐1‐iodocyclopentadienyl)manganese(I), [Mn(C₅H₄I)(CO)₃], (I), and tricarbonyl(η⁵‐1‐iodocyclopentadienyl)rhenium(I), [Re(C₅H₄I)(CO)₃], (III), are isostructural and isomorphous. The compounds [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylmanganese(I)] or bis(cymantrenyl)acetylene, [Mn₂(C₁₂H₈)(CO)₆], (II), and [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylrhenium(I)], [Re₂(C₁₂H₈)(CO)₆], (IV), are isostructural and isomorphous, and their molecules display inversion symmetry about the mid‐point of the ligand C[triple‐bond]C bond, with the (CO)₃M(C₅H₄) (M = Mn and Re) moieties adopting a transoid conformation. The molecules in all four compounds form zigzag chains due to the formation of strong attractive I...O [in (I) and (III)] or π(CO)–π(CO) [in (I) and (IV)] interactions along the crystallographic b axis. The zigzag chains are bound to each other by weak intermolecular C—H...O hydrogen bonds for (I) and (III), while for (II) and (IV) the chains are bound to each other by a combination of weak C—H...O hydrogen bonds and π(Csp²)–π(Csp²) stacking interactions between pairs of molecules. The π(CO)–π(CO) contacts in (II) and (IV) between carbonyl groups of neighboring molecules, forming pairwise interactions in a sheared antiparallel dimer motif, are encountered in only 35% of all carbonyl interactions for transition metal–carbonyl compounds.     

2,6‐Bis(azaindole)pyridine: reactivity with iron(III) and copper(II) salts

1‐[6‐(1H‐Pyrrolo[2,3‐b]pyridin‐1‐yl)pyridin‐2‐yl]‐1H‐pyrrolo[2,3‐b]pyridin‐7‐ium tetrachloridoferrate(III), (C₁₉H₁₄N₅)[FeCl₄], (II), and [2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl‐κN⁷)pyridine‐κN]bis(nitrato‐κO)copper(II), [Cu(NO₃)₂(C₁₉H₁₃N₅)], (III), were prepared by self‐assembly from FeCl₃·6H₂O or Cu(NO₃)₂·3H₂O and 2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl)pyridine [commonly called 2,6‐bis(azaindole)pyridine, bap], C₁₉H₁₃N₅, (I). Compound (I) crystallizes with Z′ = 2 in the P space group, with both independent molecules adopting a trans–trans conformation. Compound (II) is a salt complex with weak C—H...Cl interactions giving rise to a zigzag network with π‐stacking down the a axis. Complex (III) lies across a twofold rotation axis in the C2/c space group. The Cu^II center in (III) has an N₃O₂ trigonal–bipyramidal environment. The nitrate ligand coordinates in a monodentate fashion, while the bap ligand adopts a twisted tridentate binding mode. C—H...O interactions give rise to a ribbon motif.     

Synthesis of 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide

The reaction of methyl 2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate ( 1 ) with methanesulfonamide gave methyl 2-[(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridine-carboxylate ( 2 ). Alkylation of compound 2 with methyl iodide followed by cyclization of the resulting methyl 2-[methyl(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridinecarboxylate ( 3 ) yielded 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 4 ). The reaction of compound 4 with α,2,4-trichlorotoluene, methyl bromopropionate, methyl iodide, 3-trifluoromethylphenyl isocyanate, phenyl isocyanate and 2,4-dichloro-5-(2-propynyloxy)phenyl isothiocyanate gave, respectively, 4-[(2,4-dichlorophenyl)methoxy]-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazine 2,2-dioxide ( 5 ), methyl 2-[[1-methyl-2,2-dioxido-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4-yl]oxy]propanoate ( 6 ), 1,3,3-trimethyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 7 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-[3-(trifluoromethyl)phenyl]-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 8 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-phenyl-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 9 ) and N-[2,4-dichloro-5-(2-propynyloxy)phenyl]-4-hydroxy-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2] thiazine-3-carboxamide 2,2-dioxide ( 10 ).     

Syntheses and crystal structures of copper(II) complexes derived from 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Treatment of freshly precipitated Cu(OH)₂?·?xH₂O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with oxalic and malonic acids in methanol-water at room temperature gave [Cu(tptz)(C₂O₄)(H₂O)]?·?4H₂O (1) and [Cu(pma)(C₃H₂O₄)(H₂O)]?·?H₂O (2) (pma?=?2-aminocarbonylpyridine), respectively. Reaction in the absence of any acid resulted in [Cu(bpca)(tca)]?·?2H₂O (3) (bpca?=?bis(2-pyridylcarbonyl)amide anion; tca?=?2-pyridinecarboxylate anion). Complex 1 consists of [Cu(tptz)(C₂O₄)(H₂O)] and lattice H₂O molecules; the tridentate tptz ligand, bidentate oxalate dianion and an aqua ligand are bound to Cu with distorted octahedral geometry. Complex 2 is composed of [Cu(pma)(C₃H₂O₄)(H₂O)] and lattice H₂O molecules; the bidentate 2-aminocarbonylpyridine ligand, a bidentate malonate dianion and an aqua ligand are coordinated to Cu with a slightly distorted square pyramidal geometry. Complex 3 consists of [Cu(bpca)(tca)] and lattice H₂O molecules. Square pyramidally coordinated Cu atoms are surrounded by tridentate bpca with nitrogen donor atoms and a bidentate 2-pyridinecarboxylate anion.     

Bulky Arylgallium and Indium Derivatives with Co(CO)4 and Mn(CO)5 Substituents

Further investigation of the reaction of Ar*GaCl₂ (Ar* = 2,4,6-t-Bu₃C₆H₂) with Na[Mn(CO)₅] resulted in the new compound, [Ga(Ar*){Mn(CO)₅}₂] 2 . The new indium compounds, [In(Ar*){Co(CO)₄}₂] 3 and [In(Ar*){Mn(CO)₅}₂] 4 , have been prepared by the treatment of Ar*InBr₂ with Na[Co(CO)₄] and Na[Mn(CO)₅], respectively. The structure of 3 was established by single-crystal X-ray diffraction: space group P1 (No. 2), Z = 2, a = 8.625(1) Å, b = 10.557(2) Å, c = 17.55(2) Å, α = 88.43(1)°, β = 83.45(1)°, γ = 71.14(1)°. The X-ray crystal structure of [Ga{Mn(CO)₅}₃] is also reported: space group Pbca (No. 61), Z = 8, a = 12.83(3) Å, b = 11.753(2) Å, c = 29.662(6) Å, α = β = γ = 90°.