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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 146 Reactions of Tetrazadiborinanes with Heterocumulenes: Pseudodipolar [2 + 3]-CycloadditionsCO2, COS, and CS2 scavenge the 1,3-dipolar unit \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} from the tetrazadiborinanes 3. [2 + 3]-Cycloadducts are formed in a pseudodipolar reaction, namely oxadiaza- and thiadiazaborolidines of type 7, 8 and 4. A reaction mechanism is suggested.  -  The thiadiazaborolidine 4b contains a planar five-membered ring according to an X-ray structure determination. Short BN, NN, and CN bond distances suggest a heteroaromatic ring system. High polarity is associated with the thioxo group. In contrast, the oxadiazaborolidinones 8a, b are in an equilibrium with their dimers in solution.
    Notes: CO2, COS und CS2 fangen aus den Tetrazadiborinanen 3e) den 1,3-Dipol \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R'}\mathop {{\rm B - }}\limits^ \oplus {\rm NR - }\mathop {\rm N}\limits^{\rm \Theta } {\rm R} $\end{document} ab. In einer pseudodipolaren Reaktion bilden sich als [2 + 3]-Cycloaddukte die Oxadiaza- und Thiadiazaborolidine 7, 8 und 4. Ein Reaktionsmechanismus wird diskutiert.  -  Nach Röntgenstrukturanalyse enthält 4b einen planaren Fünfring. Kurze BN-, NN- und CN-Abstände legen ein heteroaromatisches System nahe, wobei der Thioxo-Gruppe eine erhebliche Polarität zuzuweisen ist. Die Oxadiazaborolidinone 8a, b stehen in Lösung im Gleichgewicht mit ihrem Dimeren.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2030-2043 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 152. 1,3,2,4-Diazaphosphaboretidines and 1,3,2,4-Diazasilaboretidines Prepared via Intra- and Intermolecular Cyclocondensation1,3,2,4-Diazaphospha(sila)boretidines 5 and 9 are accessible via thermal decomposition of compounds of type E(NR′—BR2)2 (8) or from organoboron dihalides or boron trihalides and E(NR′Li)2 [E = Si(CH3)2, CH3(O)P, R(S)P, CH3P]. The formation of 1,3-di-tert-butyl-4-methyl-(or ethyl)-1,3,2,4-diazaphospha(sila)boretidines from the precursor E(NR′—BR2)2 proceeds by an intramolecular cyclocondensation. NMR data reveal less shielded B and P atoms in the new heterocycles as compared with noncyclic compounds; this is attributed to a strained ring system. A tetracoordinated as well as a tricoordinated boron atom is observed in CH3(O)P(NR′BR2)2 compounds resulting from intramolecular BO coordination.
    Notes: 1,3,2,4-Diazaphospha(sila)boretidine 5 und 9 sind über die thermische Zersetzung von Verbindungen des Typs E(NR′-BR2)2 (8) oder durch Umsetzung von Organylbordihalogeniden bzw. Bortrihalogeniden mit N-Lithio-Verbindungen E(NR′Li)2 [E = Si(CH3)2, CH3(O)P, R(S)P, CH3P] zugänglich. Es wird gezeigt, daß die 1,3-Di-tert-butyl-4-methyl-bzw. -4-ethyl-1,3,2,4-diazaphospha(sila)boretidine aus der Vorstufe E(NR′-BR2)2 durch eine intramolekulare Cyclokondensation entstehen. Nach NMR-Daten sind die Bor- und Phosphor-Kerne in den Vierring-Heterocyclen als Folge der Ringspannung schlechter abgeschirmt als in nichtcyclischen Derivaten. Vierfach koordiniertes Bor liegt neben dreifach koordiniertem in den Verbindungen CH3(O)P-(NR′BR2)2 vor. Dies geht auf intramolekulare BO-Koordination zurück.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 1361-1373 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 169. Sterically Demanding N-Lithioaminoboranes: Reagents for the Synthesis of Symmetrically and Unsymmetrically Substituted DiborylaminesN-Metalation of R2BNH2 or R2BNMeH yields lithium amides R2BNR′Li with sterically demanding R groups (R = tBu, iPr). These compounds are synthons for symmetrically or unsymmetrically substituted diborylamines as well as for B-functional diborylamines. NMR data reveal the conformation of these diborylamines. Compounds of the type tBu2B—NMe—BR2 contain tBu2B groups whose BC2 plane stands nearly orthogonal to the B2NC skeleton. In contrast, the BRX group in diborylamines of the type tBu2B—NH—BRX is strongly twisted with respect to the B2NH plane.
    Notes: Durch N-Metallierung erhältliche Lithiumamide R2BNR′Li mit sperrigen Substituenten R = tBu, iPr eignen sich sowohl zur Darstellung symmetrisch und unsymmetrisch substituierter Diborylamine als auch zur Gewinnung B-funktioneller Diborylamine. Kernresonanzspektroskopische Untersuchungen zeigen, daß Diborylamine tBu2B—NMe—BR2 eine tBu2B-Gruppe enthalten, deren BC2-Ebene weitgehend orthogonal zur B2NC-Gerüstebene steht. In Diborylaminen tBu2B—NH—BRX ist hingegen die BRX-Gruppe gegen die B2NH-Ebene verdrillt.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 3253-3267 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 179.  -  Synthesis, Conformation, and Molecular Structure of Sterically Crowded Aminomethyleneborane PrecursorsNucleophilic substitution of one halogen atom in (tetramethylpiperidino)boron dihalides, tmpBX2 (X=F, Cl, Br) by metal organyls is determined primarily by steric factors. Replacement of one F-atom by an isopropyl or a (trimethylsilyl)methyl group to yield boranes of type tmpB(F)R present no problem. However, Cl or Br atoms cannot be substituted. Similarly, LiCHPh2 reacts with tmpBX2 to produce tmpB(X)CHPh2, but LiC(SiMe3)Ph2 can substitute only one fluorine atom in tmpBF2, while the p-substituted borane 3 is obtained by using tmpBCl2. Comparable results were achieved with 9-lithiofluorene yielding the boranes 4a-c. In contrast, 9-lithio-9-(trimethylsilyl)fluorene reacts only with tmpBF2 to produce 4f. NMR data of 4a suggest an anti orientation of the F-atom and the 9H-atom of the fluorene unit, ascertained by its X-ray molecular structure. In contrast, the trimethylsilyl derivative 4f adopts a syn geometry.
    Notes: Die nucleophile Substitution eines Halogen-Atoms in (Tetramethylpiperidino)bordihalogeniden, tmpBX2 (X=F, Cl, Br) durch Metallorganyle wird vor allem durch sterische Faktoren bestimmt. Der Ersatz eines F-Atoms durch eine Isopropyl- oder (Trimethylsilyl)-methyl-Gruppe zu tmpB(F)R-Verbindungen gelingt problemlos, jedoch unterbleibt die Umsetzung bei Verwendung von tmpBCl2 oder tmpBBr2. LiCHPh2 reagiert mit tmpBX2 zu tmpB(X)CHPh2; mit LiC(SiMe3)Ph2 gelingt die Substitution aber nur mit tmpBF2. Im Fall von tmpBCl2 erhält man das p-substituierte Boran 3. Zu vergleichbaren Ergebnissen führt 9-Lithiofluoren; man erhält die Borane 4a-c. 9-Lithio-9-(trimethylsilyl)fluoren reagiert wieder nur mit tmpBF2 und liefert 4f. NMR-Daten legen für 4a eine anti-Stellung des Fluor-Atoms zum 9H-Atom der Fluorenyl-Gruppe nahe, die durch Röntgenstrukturanalyse gesichert wurde. In 4f steht die Me3Si-Gruppe jedoch syn zum Fluor-Atom.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 863-865 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [2 + 2] Cycloaddition of the aminoiminoborane 1 with Cp2-Ti=CH2 yields a blue 1-aza-2-bora-4-titanacyclobutane derivative 2. In contrast, Fischer carbenes (CO)5M = C(OMe)Me (M=Cr, W) react in a complex way to produce 1 · M(CO)5 (4), tmpB(NHCMe3)OMe (5), and the borylated acetylene derivative 6.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 907-909 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The deprotonation of bis(diorganylboryl)amines with strong bases proceeds in most cases by BN bond cleavage. However, tBu2B-NH - BtBu2 (8) reacts with tBuLi TMEDA to produce the diborylamide 9. According to IR data, this anion possesses a linear structure in analogy with an allene.
    Notes: Die Deprotonierung von Bis(diorganylboryl)aminen mit starken Basen wird in den meisten Fällen von einer BN-Bindungsspaltung begleitet. tBu2B-NH - BtBu2 (8) reagiert mit tBuLi TMEDA unter Deprotonierung zu dem Diborylamid 9, das nach dem IR-Spektrum eine lineare, Allen-analoge Struktur besitzt.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1371-1372 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions of the Chemistry of Boron, 192. - Reactions of Mercury Dihalides and Mercury Dicyanide with an AminoiminoboraneThe aminoiminoborane 1 reacts with HgCl2 and Hg(CN)2 with insertion into the HgCl and HgC bond, respectively. Mercury amides of type 2 are obtained. In contrast, HgBr2 and HgI2 yield 1:1 adducts of the allene type 3. The new compounds were characterized by IR and NMR spectroscopy.
    Additional Material: 1 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 338-348 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 166. NMR and He(I) PE Spectroscopic Studies on Diisopropyl- and Di-tert-butylboranesNMR data (1H, 11B, 13C, 14N) of a series of diisopropyl- and di-tert-butylboranes indicate that the former correspond favourably with dimethyl- and diethylboranes. Steric effects, therefore, are not very pronounced. However, di-tert-butyl(diorganylamino)boranes deviate from a planar C2BNC2 conformation; the more bulky the R2N group the stronger is the deviation, approaching an orthogonal conformation. He(I) photoelectron spectra confirm the conclusions drawn from NMR data.
    Notes: Die kernresonanzspektroskopischen Daten (1H, 11B, 13C, 14N) einer Reihe von Diisopropyl- und Di-tert-butylboranen belegen, daß erstere mehr den Dimethyl- und Diethylboranen entsprechen, sterische Effekte somit nur einen geringen Einfluß haben. Diese kommen hingegen bei Di-tert-butyl(diorganylamino)boranen zum Tragen. Mit zunehmender Sperrigkeit der Amino-Gruppe wird eine orthogonale Einstellung der R2N-Gruppe zur C2BN-Ebene angestrebt. He(I)-PE-Spektren bestätigen die aus NMR-Daten abgeleiteten Folgerungen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 2554-2556 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 158. Addition Compounds of Aluminium and Gallium Halides with an Amino Imino Borane(tert-Butylimino)(2,2,6,6-tetramethylpiperidino)borane (4) adds AlCl3, AlBr3, or GaCl3 at the tert-bytylimino group generating adducts 5a - c which retain the dicoordinated boron atom.
    Additional Material: 1 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2681-2685 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 170. Synthesis and Structure of a 1,3,2,4-DiphosphadiboretaneDehydrohalogenation of chloro[(1,1-diethylpropyl)phosphino](2,2,6,6-tetramethylpiperidino)borane (1) produces no compound with a PB double bond but its diphosphadiboretane dimer 3, whose crystal structure has been determined. The molecule has a crystallographic center of symmetry. Its BP bond lengths (1.916, 1.933 Å) are comparatively long, suggesting weak BP bonds.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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