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161.
Synthesis and Structural Studies of Aluminum Dialkylamines and Dialkylamides: N‐Chirality of (CH3)3AlNHRR′ and cis‐trans ‐Isomerism at X2AlNRR′ (X = CH3, Cl, H) Aluminum dialkylamines and dialkylamides were prepared from Al(CH3)3 and NH(CH3)R′ (R′: –C2H5, –tC4H9) and characterized by elemental analyses, 1H‐, 13C‐, and 27Al‐NMR spectroscopy. The crystal structures of [(CH3)2AlN(CH3)(–tC4H9)]2 ( IV ), [Cl2AlN(CH3)(C2H5)]2 ( V ), and [H2AlN(CH3)(C2H5)]∞ ( VI‐trans and VI‐cis ) are discussed. 相似文献
162.
Synthesis and Structure of Ammine and Amido Complexes of Iridium The reaction of (NH4)2[IrCl6] with NH4Cl at 300 °C in a sealed glass ampoule yields the iridium(III) ammine complex (NH4)2[Ir(NH3)Cl5], which crystallizes isotypically with K2[Ir(NH3)Cl5] in the orthorhombic space group Pnma with Z = 4, and a = 1350.0(2); b = 1028.5(3); c = 689.6(2) pm. The reaction of (NH4)2[IrCl6] with NH3 at 300 °C, however, gives the already known [Ir(NH3)5Cl]Cl2 beside a small amount of [Ir(NH3)4Cl2]Cl2. In pure form [Ir(NH3)5Cl]Cl2 is obtained by ammonolysis of (NH4)2[Ir(NH3)Cl5] at 300 °C with NH3. [Ir(NH3)4Cl2]Cl2 crystallizes triclinic (P1, Z = 1, a = 660,2(3); b = 680,4(3); c = 711,1(2) pm; α = 103,85(2)°, β = 114,54(3)°, γ = 112,75(2)°). The structure contains Cl– anions and [Ir(NH3)4Cl2]2+ cations with a trans position of the Cl atoms. Upon reaction of [Ir(NH3)5Cl]Cl2 with Cl2 one ammine ligand is eliminated yielding [Ir(NH3)4Cl2]Cl, which is transformed to orthorhombic [Ir(NH3)4(OH2)Cl]Cl2 (Pnma, Z = 4, a = 1335,1(3); b = 1047,9(2); c = 673,4(2) pm) by crystallization from water. In the octahedral complex [Ir(NH3)4(OH2)Cl]2+ the four ammine ligands have an equatorial position, whereas the Cl atom and the aqua ligand are arranged axial. Oxidation of (NH4)2[Ir(NH3)Cl5] with Cl2 at 330 °C affords the tetragonal IrIV complex (NH4)[Ir(NH3)Cl5] (P4nc, Z = 2, a = 702.68(5); c = 912.89(9) pm). Its structure was determined using the powder diagram. Oxidation of (NH4)2[Ir(NH3)Cl5] with Br2 in water, on the other hand, gives (NH4)2[IrBr6] crystallizing in the K2[PtCl6] type. Oxidation of (PPh4)2[Ir(NH3)Cl5] with PhI(OAc)2 in CH2Cl2 affords the IrV amido complex (PPh4)[Ir(NH2)Cl5]. 相似文献
163.
Stefan Sahli Brian Frank W.Bernd Schweizer Franois Diederich Denise Blum‐Kaelin JohannesD. Aebi Hans‐Joachim Bhm Christian Oefner GlennE. Dale 《Helvetica chimica acta》2005,88(4):731-750
A new class of nonpeptidic inhibitors of the ZnII‐dependent metalloprotease neprilysin with IC50 values in the nanomolar activity range (0.034–0.30 μM ) were developed based on structure‐based de novo design (Figs. 1 and 2). The inhibitors feature benzimidazole and imidazo[4,5‐c]pyridine moieties as central scaffolds to undergo H‐bonding to Asn542 and Arg717 and to engage in favorable π‐π stacking interactions with the imidazole ring of His711. The platform is decorated with a thiol vector to coordinate to the ZnII ion and an aryl residue to occupy the hydrophobic S1′ pocket, but lack a substituent for binding in the S2′ pocket, which remains closed by the side chains of Phe106 and Arg110 when not occupied. The enantioselective syntheses of the active compounds (+)‐ 1 , (+)‐ 2 , (+)‐ 25 , and (+)‐ 26 were accomplished using Evans auxiliaries (Schemes 2, 4, and 5). The inhibitors (+)‐ 2 and (+)‐ 26 with an imidazo[4,5‐c]pyridine core are ca. 8 times more active than those with a benzimidazole core ((+)‐ 1 and (+)‐ 25 ) (Table 1). The predicted binding mode was established by X‐ray analysis of the complex of neprilysin with (+)‐ 2 at 2.25‐Å resolution (Fig. 4 and Table 2). The ligand coordinates with its sulfanyl residue to the ZnII ion, and the benzyl residue occupies the S1′ pocket. The 1H‐imidazole moiety of the central scaffold forms the required H‐bonds to the side chains of Asn542 and Arg717. The heterobicyclic platform additionally undergoes π‐π stacking with the side chain of His711 as well as edge‐to‐face‐type interactions with the side chain of Trp693. According to the X‐ray analysis, the substantial advantage in biological activity of the imidazo‐pyridine inhibitors over the benzimidazole ligands arises from favorable interactions of the pyridine N‐atom in the former with the side chain of Arg102. Unexpectedly, replacement of the phenyl group pointing into the deep S1′ pocket by a biphenyl group does not enhance the binding affinity for this class of inhibitors. 相似文献
164.
Gintaras Pivoriunas Ccilia Maichle‐Mssmer Simon Schwarz Joachim Strhle 《无机化学与普通化学杂志》2005,631(10):1743-1745
Synthesis and Crystal Structure of [(Ph3PAu)3NPPh3][PF6]2, a Gold(I) Phosphoraneiminato Complex The photolytic reaction of Ph3PAuN3 with Cr(CO)6 in THF yields the phosphoraneiminato complex [(Ph3PAu)3NPPh3]2+ in low yield as well as the cluster cation [(Ph3PAu)8]2+ as the main product. The phosphoraneiminato complex crystallizes from CH2Cl2 with [PF6]? ions as [(Ph3PAu)3NPPh3][PF6]2·CH2Cl2 in the triclinic space group with a = 1200.8(1), b = 1495.6(2), 2053.5(5), α = 86.97(2)°, β = 82.79(1)°, γ = 81.87(2)°, and Z = 2. The phosphoraneiminato ligand bridges through its N atom three Au atoms, which itself are connected to each other by weak aurophilic interactions. 相似文献
165.
166.
167.
168.
Andr Müller Walter Keller-Schierlein Jacek Bielecki Gabriele Rak Joachim Stümpfel Hans Zhner 《Helvetica chimica acta》1986,69(8):1829-1832
(2S, 3R, 4R, 6R)-2,3,4-Trihydroxy-6-methylcyclohexanone from Two Strains of Actinomycetes A tetrazolium-blue positive compound was isolated from two strains of acinomycetes. Its constitution and relative configuration 1 were determined by spectroscopic methods, and the absolute configuration by degradation to (+)-(R)-methylsuccinic acid. 相似文献
169.
Gerd-Volker Rschenthaler Rainer Bohlen Rudolph Francke Joachim Heine Reinhard Schmutzler 《无机化学与普通化学杂志》1986,533(2):18-22
Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenol The monocyclic phosphorane (EtO)3P[OC(CF3)2C(CF3)2O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4 . The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me3SiO)2P(O)OC(CF3)2C(CF3)2OSiMe3 8 in the reaction of 3 and 4 with Me3SiCl/(Me3Si)2NH. (Me3SiO)3P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5 , but the phosphonate 11 which gave (Me3SiO)2P(O)OC(CF3) ? CF2 12 upon heating with the loss of fluorotrimethylsilane. 相似文献
170.
Reza Kordnezhadian Bing-Yu Li Armir Zogu Dr. Joachim Demaerel Prof. Dr. Wim M. De Borggraeve Dr. Ermal Ismalaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201491
Pentafluorosulfanyl (SF5)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF5 bond formation as well as the use of SF5-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF5 group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015. 相似文献