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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 375-379 
    ISSN: 0009-2940
    Keywords: Cyclophanes / Hostguest chemistry / Macrocyclic compounds / Phanes / Supramolecular chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Watersoluble Macrobicyclic CavitiesThe watersoluble macrobicyclic compounds 1, 3, 5a, and 5b have been synthesized for the first time bearing large endolipophilic cavities of different sizes and shapes. They were studied with respect to their interactions towards lipophilic guest compounds. The “in/out” isomerism of the hitherto largest endolipophilic cavities 4a, 4b, 5a, and 5b has been investigated by 1H-, 13C-NMR spectroscopy and FAB mass spectrometry. The absence of significant 1H-NMR high-field shifts in hostguest studies is attributed to the rigidity of cavities 1 and 3, whilst the isomeric cavities 5a and 5b contain very large openings. Orientational fluorescence spectroscopy investigations, however, suggest hostguest interactions of the isomers 5a and 5b with ammonium 8-anilino-1-naphthalenesulfonate (8,1-ANS).
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 859-867 
    ISSN: 0009-2940
    Keywords: Crown compounds / Host-guest chemistry / Macropentacyclic compounds / Phanes / Supramolecular chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentamacrocyclic Tris-Crown Hosts. - Selective Binding of Cationic, Anionic, and Neutral Guest CompoundsThe tris-crown host compounds 1-4 were synthesized for the first time. The X-ray crystal structures of 2 and of the 1:3 complex of 1 and KSCN were determined. Whereas in the free crown 2 a less well preorganized molecular cavity is encountered, in the complex of 1 with KSCN one potassium ion is bound to each crown ether unit. One of the three SCN- anions is situated in the interior of the cavity and in addition is disordered in such a way as to be bound to the K+ using partially the S atom of the SCN- ion. Organic guest molecules like 1,2-, 1,3-, 1,5-, 2,6-, and 2,7-naphthalenediol as well as β-naphthol in acidic water solution are bound selectively in the interior of the cavities of the host molecules 2 and 3, but not by 1 and 4, the cavities of which seem to be too small and too large, respectively. In contrast, the binding of α-naphthol and of smaller phenolic guest molecules like phenol, resorcinol, pyrocatechol, phloroglucinol, pyrogallol, and 1,2,4-trihydroxy-benzene with the host 1-4 is much less pronounced (1H- NMR highfield shifts).
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1001-1004 
    ISSN: 0009-2940
    Keywords: Amino acid complexes ; L-Glutamate complexes ; Hydrogen L-glutamate complexes ; Potassium hydrogen L-glutamate ; Hydrogen bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compound is obtained by neutralization of aqueous solutions of L-glutamic acid with potassium hydroxide, and crystallization from aqueous methanol. The compound shows a pH of 7 in water at ambient temperature and an optical rotation [α]20D of -4.30 (c = 3.0). In the crystal (orthorhombic, space group P212121) the potassium ion is in a distorted trigonal-prismatic environment of six oxygen atoms of four different amino acids and of the water molecule. No nitrogen coordination is observed. Through the bridging function of some of the α-carboxylate oxygen atoms (O1, O2) and through complexation of the metal through the γ-carboxylate groups (O3), a layer-coordination polymer, with strings of potassium ions running parallel, is formed. The layers are cross-linked by hydrogen bonds involving the ammonium and γ-carboxylate functions as well as the water molecule.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0009-2940
    Keywords: Gold(I) complex ; Phosphine (selenide) complexes ; Aus···Au interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [(CO)AuCl] reacts with equimolar amounts of Ph2PCH2P(Se)Ph2 (dpmSe) to afford ClAuPh2PCH2P(Se)Ph2, in which dpmSe is bound to gold in a monodentate fashion by phosphorus. Subsequent reaction of this 1:1 complex with AgClO4 results in the formation of the 10-membered ring complex 4 which crystallizes in the monoclinic space group P21/n with approximately centrosymmetric dicationic units, in which two gold (I) atoms are doubly bridged by two dpmSe ligands coordinated by phosphorus and selenium. The coordination at the gold atoms deviates from linearity and implies an Au···Au interaction with the gold(I) atoms separated by a distance of 3.020(1) Å.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0009-2940
    Keywords: Bases, concave / Protonation, regioselective / Nef reaction / aci-Nitro compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intramolecular competition for C- or O-protonation of the nitronate anion 5a is determined by sterical factors and by the [EtOH⊕2] concentration. The product of the Nef reaction 6 is formed in buffered, non-acidic media when the proton donors are sterically hindered.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 285-287 
    ISSN: 0009-2940
    Keywords: Phosphanes, primary / Gold complexes / Gold-gold interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (CO)AuCl reacts with (2,4,6-trialkylphenyl)phosphanes 1a-d (alkyl = Me, Et, iPr, tBu) to give the 1:1 complexes 2a-d. The crystal structure of 2d shows pairs of molecules with Au…Au contacts of 3.440(1) Å.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 643-645 
    ISSN: 0009-2940
    Keywords: Concave base / Macrocycle / 1,10-Phenanthroline / Cyclophane / Aryl lithium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of lithium aryls 3 to 1,10-phenanthroline (2), functionalization of the rearomatized bisadduct 8b to the tetraphenol 8d, and cyclization of 8d with two equivalents of an α,ω-ditosylate 9 led to a highly symmetrical, conformer-free bimacrocyclic 1,10-phenanthroline 10a in which the basic and coordinating region possesses a concave shielding.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1221-1226 
    ISSN: 0009-2940
    Keywords: π-Complexes of p-block elements ; Arene complexes ; Arsenic complexes ; Antimony complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2,4,5-Tetramethyl-and pentamethylbenzene from stable 1:2 complexes with SbCl3 of the type (C6H6-Men) · 2SbCl3(1,2) with an inverse sandwich structure. The compounds crystallize isotypically and are isostructural to the (hexamethylbenzene)antimony and -bismuth complexes.They are thus built of tetrameric chlorine-bridged Sb4Cl12 units, which are crosslinked at the metal centers with four other tetramers by double-sided arene coordination (X-ray structure analysis of 1). The Sb atoms, which are in a distorted trigonal bipyramidal environment, show a slight deviation from a centric (η6) coordination. The same stoichiometry and the same structural principle are found for the complex (C6Me6 · 2 AsCl3 (4), which is obtained from solutions of hexamethylbenzene and AsCl3 in toluene. In 4 the arsenic atoms are η6-coordinated to the hexamethylbenzene ring from both sides (X-ray analysis). Treatment of AsBr3 with hexamethylbenzene leads to a product of the composition 5 (C6Me6) · AsBr3. Reaction of hexaethylbenzene with AsCl3 in petroleum ether leads to the formation of the 1:2 complex (C6Et6) · 2 AsCl3 (5), built of discrete inverse sandwich units, which are arranged in strings parallel to the crystallographic c axis. From solutions of AsCl3 (AsBr3), SbCl3 (SbBr3) and hexaethylbenzene in petroleum ether ternary compounds are isolated with an As:Sb ratio of 1:5.2 and 1:1.86, respectively. Single crystal X-ray structure determinations failed as a consequence of severe disorder.
    Additional Material: 4 Ill.
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  • 9
    ISSN: 0009-2940
    Keywords: Dihydroanthracene ; Dihydroanthracene, butyl-substituted ; Tricarbonylchromium ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes [9,10-dihydroanthracene][tricarbonylchromium]n [9,10-DHA][Cr(CO)3]n [n = 1 (1), 2 (2)] and the related mono- and bis(tricarbonylchromium) complexes of 2,6- and 2,7-di-tert-butyl-9,10-dihydroanthrancene [2,6-DB-9,10-DHA][Cr(CO)3]n [n = 1 (3), 2 (4)] and [2,7-DB-9,10-DHA][Cr(CO)3]n [n = 1 (5), 2 (6)] have been prepared by heating the 9,10-DHA species in the presence of hexacarbonylchromium [Cr(CO)6]. Evidence for the existence of the complex [2,6,9-tri-tert-butyl-9,10-DHA][Cr(CO)3] (7) is also presented. The complexes have been characterised spectroscopically, and for complex 1 an X-ray crystallographic structure determination has been carried out. This complex adopts the unexpected structure in which the non-coordinated arene ring is bent towards the Cr(CO)3 moiety. The syntheses and spectroscopic characterisations of 2,6- and 2,7-di-tert-butylanthracene (2,6- and 2,7-DBA), 2,6- and 2,7-di-tert-butyl-9,10-dihydroanthracene (2,6-and 2,7-DB-9,10-DHA), 2,6,9-, 2,7,9-, and 2,7,10-tri-tert-butyl-9,10-dihydroanthracene (2,6,9-, 2,7,9- and 2,7,10-TB-9,10-DHA), and 2,6,9,10- and 2,7,9,10-tetra-tert-butyl-9,10-dihydroanthracene(2,6,9,10- and 2,7,9,10-TeB-9,10-DHA) are also given.
    Additional Material: 6 Ill.
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  • 10
    ISSN: 0009-2940
    Keywords: Arene complexes / Antimony(III) complexes / Organoantimony compounds / Dihydroanthracene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystals of a 1:2 complex of 9,10-dihydroanthracene and antimony tribromide are obtained from toluene solutions of the components. In the crystal the complex forms corrugated sheets of an inorganic (SbBr3)n coordination polymer, which are cross-linked by antimony coordination to the benzene rings of the dihydroanthracene molecules are also arranged in folded layers. The dihydroanthracene molecules reside on centers of inversion and their carbon skeleton is planar within the limits of the experiment. With contacts from opposite sides of the molecular plane, the dihydroanthracene is η6,(η6)'-coordinated to the Sb(III) centers at distances of 3.25 Å. In a very irregular geometry the coordination sphere of the crystallographically equivalent antimony atoms contains bromine neighbours at different distances. - Antimony trichloride and dihydroanthracene form a complex of ambiguous stoichiometry, while bismuth trichloride again gives a 2;1 complex, the structure of which has not yet been determined.
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