Azov, Vladimir

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Preferred name
Azov, Vladimir
Official Name
Azov, Vladimir
Alternative Name
Azov, Vladimir A.
Azov, V. A.
ORCID
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    Item-typ:Veröffentlichung,
    Silylierte Corannulene
    (2014-11-28)
    Hesse, Maxie
    ;
    Azov, Vladimir
    ;
    Beckmann, Jens
    ;
    Beckmann, Jens
    In the first part of this thesis a new synthetic route to silylated corannulenes is presented. It includes the new compounds 8-bromo-1,6,7,10-tetramethylfluoranthene (10), 8-trimethylsilyl-1,6,7,10-tetramethylfluoranthene (11), 7-bromomethyl-8-trimethylsilyl-1,6,10-tri(dibromomethyl)methylfluoranthene (13) und 4-trimethylsilyl-1,2,6-tribromocorannulene (14). The second part deals with the synthesis of the organo boronic acids dimetyl-(di-p-phenylboronic acid) silane (19) und 4-(dimethylsilyl)phenylboronic acid (20) and a potentially buckycatcher molecule, namely di-p-corannulenylphenyl (dimethyl) silane (22) which shows indications for the interaction with C60 molecules. In the last part the results of quantum mechanical calculations of the bowl depths and the bowl-to bowl inversion energies using different methods (DFT(B3LYP, M06-2X), MP2) and basis sets (6-311 G(2d,p), cc-pVDZ und cc-pVTZ) of a selection of substituted silylated corannulene derivatives are discussed.
    Dissertation
      217  99
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    Item-typ:Veröffentlichung,
    Von multifunktionalen, siliziumorganischen Bausteinen zu Pinzetten-stabilisierten Silylkationen
    (2015-02-06)
    Denhof, Andreas
    ;
    Azov, Vladimir
    ;
    Beckmann, Jens
    ;
    Beckmann, Jens
    Starting with 1,3-Dihalogenebenzene new metalorganic compounds 2,6-dihalogene-1-dimethylsilylbenzenes (1a, 1b, 1c), 3-bromo-2-dimethylilyl-1-diphenylphosphinebenzene (4), 1-bromo-2-dimethylsilyl-1-diphenylphosphinochalcogenidebenzenes (4a, 4b), (3-bromo- 3-bromo-2-dimethylsilyl)phenyl)(methyl)diphenylphosphoniumiodide (4c), dimethylsilyl-1-tributylstannylbenzene(5), 2,3-bis(dimethylsilyl)-1-diphenylphosphinebenzene (6), 3,2,-bis(dimethylsilyl)-1-diphenylphosphine-3-diphenylphosphinechalcogenidbenzene (6a, 6b), 2-dimethylsilyl-1,3-bis(diphenylphosphine)benzene (7), 2-dimethylsilyl-1-diphenylphospine-3-diphenylphosphinechalcogenidebenzenes (7a, 7b), (2-(dimethylsilyl)-3-(diphenylphosphanyl)phenyl)(methal)diphenylphosphonium iodide (7c), 2-dimethylsilyl-1,3-bis(diphenylphosphinechalcogenide)benzenes (8a, 8b, 8c), (2-(dimethyllsilyl)-1,3-phenylene)bis(methyldiphenylphosphonium) diiodide (8d), 1,3-dihalogene-2-tributylstannylbenzenes (14a, 14b, 14c), bis(2,6-dihalogene-1-dimethylsilylbenzenes) (15a, 15b, 15c), 1,7-bis(diphenylphosphine)biphenylene (16), 1,7-bis(diphenylsulfidophosphine)biphenylene (17) were synthesized and characterized. This compounds were used as precursor for a variety of reactions, mainly for the preparation of new pentacoordinated silylcations 2-dimethylsilyl-1,3-diphenylphosphineoxido)phenyl tribromide (10), 2-dimethylsilyl-3-diphenylphosphin-1-diphenylsulfidophosphinepehnyl tetrakis(pentafluorophenyl)borate (11), 2-dimetrhylsilyl1,3-bis(diphenylphosphinesulfido)phenyl tetrakis(pentafluorophenyl)borate (12), 2-dimethylsilyl-3-diphenylphosphineoxido-1-diphenylphosphinesulfidophenyl tetrakis(pentafluorophenyl)borate (12a) and 2-dimethylsilyl-1,3-bis(diphenylphosphineselenido)phenyl tetrakis(pentafluorophenyl)borate (13).
    Dissertation
      256  121
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    Item-typ:Veröffentlichung,
    Siliciumhaltige Polyaryletherketone
    (2014-07-04)
    Danz, Nadine
    ;
    Azov, Vladimir
    ;
    Beckmann, Jens
    ;
    Beckmann, Jens
    PAEK is a crystalline aromatic poly(ether-ketone) and an industrially important high-performance thermoplastic with a very high thermal stability, which has found numerous applications, e.g. as material for bone replacement implants. we have found a new way to syntheses PAEK and we report on the syntheses of related hybrid polymers containing siloxane linkages [p,p'-Me2SiC6H4EC6H4SiMe2O]n (E = CO, O, S). Like the parent PAEK, the polysiloxane 1 comprising the carbonyl group is a crystalline high-melting polymer, whereas the polysiloxanes 2 and 3 containing ether and thioether groups are oils. The corresponding cyclic oligomers, namely the dimeric silacyclophanes [p,p'-Me2SiC6H4EC6H4SiMe2O]2 (E = CO, O, S) were also obtained and fully characterized by X-ray crystallography.
    Dissertation
      260  115
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    Item-typ:Veröffentlichung,
    Synthese multivalenter Organophosphonsäuren und - silanole. Neue Bausteine in der supramolekularen Chemie.
    (2013-12-13)
    Schütrumpf, Alexandra
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    Azov, Vladimir
    ;
    Beckmann, Jens
    ;
    Beckmann, Jens
    We present the Synthesis of new multifunctional organosilanols for their use in supramolecular chemistry and -phosphonic acids as linkers in metal phosphonates. The tri- and tetrasilanols benzene-1,3,5-tri-p-phenyl(hydroxydiisopropylsilane) (4), benzene-1,3,5-tri-p-biphenyl(hydroxydiisopropylsilane) (8) and tetrakis[(4-(hydroxydiisopropylsilyl)biphenyl)]silane (16) were synthesized. The supramolecular structures have been studied using the TOPOS program. For the synthesis of multivalent phosphonic acids a new synthetic route, the suzuki-coupling of 4-(Dimethoxy¬phosphoryl)phenylboronic acid to numerous aryl bromides, was established. In addition, the potentially photo switchable trans(E)-azobenzenebis(4-phosphonic acid) (31) was prepared. The luminescent phosphonic acids, anthracene-9,10-bisphosphonic acid (36), anthracen-9,10-bis(4'-phenylphosphonic acid) (38), pyrene-1,3,6,8-tetrakisphosphonic acid (40) and pyrene-1,3,6,8-tetrakis(4'-phenyl¬phosphonic acid) (42), have been synthesized and investigated by fluorescence spectroscopy. Furthermore the synthesis of the tetrahedral phosphonic acids, tetraphenylsilane-tetrakis(4-phosphonic acid) (44) and tetrabiphenylsilane-tetrakis(4-phos¬phonic acid) (47) is described. Two metal phosphonates are obtained from 44 with copper and zinc, which have been characterized by X-ray structure analysis.
    Dissertation
      254  147
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    Item-typ:Veröffentlichung,
    Functionalized Silyl-BINOLs and their Use as Building Blocks for the Synthesis of Chiral Sila-Macrocycles.
    (2012-06-01)
    Rivas King, Nelly
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    Azov, Vladimir
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    Beckmann, Jens
    ;
    Beckmann, Jens
    The axially chiral 1,1'-bi-2-naphthol (BINOL) have been used as starting material to produce chiral organosilanes in moderate to excellent yields. Among them, hydrosilanes (S)-6,6'-bis(dimethylsilyl)-2,2'-dimethoxy-1,1'-binaphthyl (26), (S)-3,3'-bis(dimethylsilyl)-2,2'-dimethoxy-1,1'-binaphthyl (30), and (S)-4,4'-bis(dimethylsilyl)-6,6'-dichloro-2,2'-dimethoxy-1,1'-binaphthyl (35) are reported. These compounds were further converted into their respective silanols, (S)-6,6'-bis(dimethylhydroxysilyl)-2,2'-dimethoxy-1,1'-binaphthalene (26a), (S)-3,3'-bis(dimethylhydroxysilyl)-2,2'-dimethoxy-1,1'-binaphthalene (30a), and (S)-6,6'-dichloro-4,4'-bis(dimethylhydroxysilyl)-2,2'-dimethoxy-1,1'-binaphthalene (35a) by oxidation in the presence of Pearlmans catalyst in water. Also, chlorination of hydrosilanes 26, 30, and 35 with carbon tetrachloride and palladium dichloride afforded chlorosilanes (S)-6,6'-bis(dimethylchlorosilyl)-2,2'-dimethoxy-1,1'-binaphthalene (26b), (S)-3,3'-bis(dimethylchlorosilyl)-2,2'-dimethoxy-1,1'-binaphthalene (30b), and (S)-6,6'-dichloro-4,4'-bis(dimethylchlorosilyl)-2,2'-dimethoxy-1,1'-binaphthalene (35b) in quantitative yields. Additionally, the synthesis and characterization of novel vinylsilanes (S)-6,6'-bis(dimethylvinylsilyl)-2,2'-dimethoxy-1,1'-binaphthalene (27), (S)-3,3'-bis(dimethylvinylsilyl)-2,2'-dimethoxy-1,1'-binaphthalene (31), and (S)-6,6'-dichloro-4,4'-bis(dimethylvinylsilyl)-2,2'-dimethoxy-1,1'-binaphthalene (36) is described. Other chiral organosilanes containing chloromethylsilane groups were synthesized, from which novel compounds bearing organotin moieties were afforded. Besides, chiral sila-macrocycles were prepared using the above mentioned chiral organosilane building blocks. Thus, cyclic siloxanes (S,S)-2,2',10,10'-tetramethoxy-1,1',9,9'-bis(binaphthyl)-6,6',14,14'-octamethyltetrasiloxane (38) and (S,S)-2,2',10,10'-tetramethoxy-1,1',9,9'-bis(binaphthyl)-3,3',11,11'-octamethyltetrasiloxane (39) were obtained from hydrosilanes (26 and 30) or silanols (26a and 30a). Novel macrocycles (S,S)-2,2',10,10'-tetramethoxy-1,1',9,9'-bis(binaphthyl)-6,6',14,14'-octamethyldiethylsilane (41) and (S,S)-2,2',10,10'-tetramethoxy-1,1',9,9'-bis(binaphthyl)-3,3',11,11'-octamethyldiethylsilane (42) possessing an aliphatic bridge were conveniently prepared via hydrosilylation reaction of vinylsilanes (27 and 31) with hydrosilanes (26 and 30) using Karstedt catalyst, respectively. In addition, chlorosilanes (26b and 30b) were used to prepare macrocycles connected by an aromatic ligand. Besides, functionalization of macrocycles 38 - 42 by demethylation, bromination, and silylation was attempted.
    Dissertation
      341  232