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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 2668-2673 
    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, 127. Hexamethylborazine-Gallium Trichloride: Structure in Solution and in the Solid StateHexamethylborazine forms a 1:1 adduct 1 with gallium trichloride. It is isostructural with hexamethylborazine-aluminium tribromide. The BN heterocycle is no longer planer, and the molecule adapts almost Cs symmetry and contains a tetracoordinated nitrogen atom. 1 shows fluctional behavior in toluene solution at room temperature. The coordinated GaCl3 will no longer change its coordination site at T 〈 220 K (two signals each for the CH3N-and CH3B-protons). However, at T 〈 195 K an additional splitting of the signals is observed - three signals for each type of CH3 groups: this would be consistent with a pentacoordinated gallium atom and a bidentate borazine ligand.
    Additional Material: 1 Ill.
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  • 2
    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, 128. Investigations on Substituent Exchange Reactions using 10B Labelling: Reactions of 1,3,2-Dithiaborolanes and Related Heterocycles with Boron TribromideThe formation of the bromo derivatives from methylated dithiaza- (3) and thiadiazadiborolidines (6) and BBr3 follows the endocyclic reaction mechanism. This holds also for the substituent exchange between some 2-bromo- (9) and 2-(dialkylamino)-1,3,2-dithiaborolanes (15, 18) as demonstrated by the use of 10BBr3. An addition of BBr3 to one of the ring sulfur atoms preceeds the substitution process. Some of these adducts were isolated and the equilibrium constants of the adduct formation were determined. 3,5-Bis(diisopropylamino)-1,2,4,3,5-trithiadiborolane (22) forms also an S-adduct with 10BBr3 (23). The substituent exchange proceeds endocyclically while the same reaction involving the 3,5-bis(dimethylamino) derivative follows the exocyclic route.
    Notes: Die Überführung der methylierten Dithiaza- (3) und Thiadiazadiborolidine (6) in die Brom-Derivate mit BBr3 folgt dem endocyclischen Substitutionsmechanismus. Gleiches gilt für den Substituentenaustausch zwischen einigen 2-Brom- (9) und 2-(Dialkylamino)-1,3,2-dithiaborolanen (15, 18), wie Umsetzungen mit 10BBr3 zeigen. Dem Substitutionsprozeß geht eine Addition des BBr3 an ein Ring-Schwefelatom voraus. Einige dieser Addukte wurden isoliert und die Gleichgewichtskonstanten der Adduktbildung bestimmt. Auch 3,5-Bis(diisopropylamino)-1,2,4,3,5-trithiadiborolan (22) bildet mit 10BBr3 ein S-Addukt (23). Dies führt zur endocyclischen Substitution, während der analoge Substitutionsprozeß bei dem 3,5-Bis(dimethylamino)-Derivat exocyclisch abläuft.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1132-1153 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrazaboles: Electrophilic Substitutions and Studies of Their Crystal and Molecular StructuresElectrophilically induced substitution reactions at the boron atoms of pyrazaboles, [R2Bpz]2, using 10BBr3 proceed without exchange of the boron atoms. All four substituents R may be exchanged for Br, with the exception of R = C2H5, and variously substituted pyrazaboles are detected by 11B NMR as intermediates. Some of these were isolated. Based on NMR data obtained for the reaction of [(C2H5)2Bpz]2 with BBr3, ionic intermediates are proposed for these exchange reactions. A stepwise interaction also occurs on treatment of the pyrazabole 1a with pyrazole; this is documented by the isolation of the monopyrazol-1-ylpyrazabole 1e.  -  The central B2N4 ring of pyrazaboles adopts a chair, a boat, or a planar conformation in the solid state as shown by X-ray structural studies on five different pyrazaboles. Therefore, packing effects seem to determine the ring conformation.
    Notes: Elektrophil induzierte Substitutionsreaktionen an den Boratomen der Pyrazabole [R2Bpz]2 mit 10BBr3 erfolgen ohne Austausch von Boratomen. Alle vier Substituenten R werden gegen Br substituiert (Ausnahme R = C2H5), wobei 11B-NMR-spektroskopisch verschieden substituierte Pyrazabole als Zwischenprodukte nachgewiesen und in einigen Fällen isoliert wurden. Dabei weisen die NMR-Daten der Umsetzung von [(C2H5)2Bpz]2 mit BBr3 auf eine ionische Zwischenstufe für diese Austauschreaktion hin. Eine schrittweise Substitution erfolgt auch bei der Umsetzung des Pyrazabols 1a mit Pyrazol, wie die Isolierung von Monopyrazol-1-ylpyrazabol 1e zeigt.  -  Nach Röntgenstrukturuntersuchungen an fünf Pyrazabolen liegt der zentrale B2N4-Ring in der Sessel-Boot- oder planaren Konformation vor. Danach scheinen Packungseffekte die jeweilige Konformation im festen Zustand zu bestimmen.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1222-1234 
    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, 1351). Addition Compounds of 1,3,2-Diazaborolidines with Aluminium and Gallium Halides1,3-Dimethyl-1,3,2-diazaborolidines 3 - 6 add aluminium and gallium halides, respectively, in a 1 : 1 molar ratio. The ligand is monodentate in these coordination compounds (3a - e, 4a, 5a, b, 6a). Addition occurs at one of the ring nitrogen atoms irrespective of the B-substituent. A consequence of this coordination is a long BN bond to the chiral tetracoordinated nitrogen atom as well as a considerable shortening of the BN bond involving the tricoordinate ring nitrogen. In addition, the almost planar five-membered ring adopts the envelope conformation as shown by an X-ray structure analysis of 5a. In contrast, the 2-(dimethylamino)diazaborolidine 7 yields unstable 1 : 1 besides stable 1 : 2 adducts 8. In these the Lewis acid is also coordinated to the ring nitrogen atoms only.
    Notes: Die 1,3-Dimethyl-1,3,2-diazaborolidine 3 - 6 addieren Aluminium- oder Galliumhalogenide im Molverhältnis 1 : 1 zu Koordinationsverbindungen 3a - e, 4a, 5a, b, 6a, in denen der Ligand einzähnig ist. Die Anlagerung erfolgt unabhängig vom B-Substituenten an einem Ringstickstoff-Atom. Folge dieser Koordination ist die Ausbildung einer langen BN-Bindung zum chiralen tetra-koordinierten Ring-Stickstoff, eine erhebliche Verkürzung der BN-Bindung zum dreifach koordinierten endocyclischen Stickstoffatom und der Übergang des nahezu planaren Fünfrings in die „envelope“-Konformation, wie die Röntgenstrukturanalyse von 5a belegt. Im Gegensatz dazu liefert das 2-(Dimethylamino)diazaborolidin 7 mit AlX3 und GaX3 instabile 1 : 1- und stabile 1 : 2-Addukte 8. In diesen ist die Lewis-Säure nur an den Ringstickstoff-Atomen koordiniert.
    Additional Material: 3 Ill.
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  • 5
    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.
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  • 6
    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.
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  • 7
    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.
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  • 8
    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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  • 9
    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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  • 10
    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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