<i>N,N′</i>‐Dilithiobis(alkylamino)phenylborane als Synthesebausteine für viergliedrige Metallacyclen

Fest, Dietmar; Habben, C.; Meller, A.; Sheldrick, George M.; Stalke, Dietmar; Pauer, Frank

doi:10.1002/cber.19901230409

Cited by 43 publications

(32 citation statements)

References 16 publications

(1 reference statement)

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“…121°C. NMR in C 6 D 6 : δ 1 H ϭ 6.36 (ddd, 3 (6). The solid that was left on concentration of the solution also showed an 11 B NMR signal at δ ϭ 23.8 in deuteriobenzene, which was assigned to 6.…”

Section: Tris(2-pyridylamino)borane (4)mentioning

confidence: 99%

“…In comparison with lithium organylamides [16,17] the tendency of the lithium (diorganylboryl)amides to associate through LiϪN bridges did not seem to be significantly altered. Dimetallation of bis-(tert-butylamino)organylboranes was reported by Meller et al, [6] whilst it is only recently that a threefold lithiation of the borazine (PhBϪNH) 3 was successfully achieved, resulting in the compound (PhBNLi) 3 ·(LiPh) 3 ·(THF) 3 , characterized by X-ray diffraction analyses. [18] N-Lithiation of triaminoboranes offers a unique chance to study the influence of electronic and steric effects.…”

Section: H 14 Li·pmdetamentioning

confidence: 99%

“…[3] As expected, (lithioamino)boranes are useful reagents for the syntheses not only of other metallated aminoboranes [2,4,5Ϫ7] by transmetallation reactions, but also for syntheses of diborylamines [8Ϫ10] and BN heterocycles. [5,6,11] So far, only a few structures of (lithioamino)boranes have been determined: the ionic [Li(-OEt 2 ) 3 ][mes 2 BϭNϭBmes 2 ], [12] the dimeric Li(OEt 2 ) 2 -NmesϪBmes 2 , [7] and the solvent-free trimeric (lithioamino)-9-borabicyclonane. [13] In the presence of chelating ligands, monomeric molecular (lithioamino)boranes, such as tBu 2 B(tBuN)Li·tmen or (Me 3 Sn)NϪBC 8 …”

Section: Introductionmentioning

confidence: 99%

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Triaminoboranes and Their Metallation toN-Lithiotriaminoboranes

Braun¹,

Habereder²,

Nöth³

et al. 2002

Eur. J. Inorg. Chem.

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In order to study the competition between deprotonation, borate formation, and B−N bond cleavage, six triaminoboranes bearing 1−3 NH functions were treated with butyllithium. The 2-anilino-1,3,2-diazaborolidine 1 was cleanly deprotonated, but the resulting N-lithio compound could not be crystallized. However, as a result of slow hydrolysis, the lithium 2-oxido derivative 7 was isolated in low yield as a dimeric ether solvate. Double deprotonation of 2-(dimethylamino)-1,3,2-benzodiazaborolidine (9) was accompanied by B−N bond cleavage. The dilithio derivative reacted with Me 3 SiCl to produce 2-dimethylamino-1,3-bis(trimethylsilyl)-1,3,2-benzodiazaborolidine (11). Similarly, dianilino(diphenylamino)borane (2) was readily deprotonated to the insoluble dilithium compound. B−N bond cleavage also occurred, however, and the solvates Ph 2 NLi·dme (13) and Ph 2 NLi·2py (14) were isolated. These are dimeric, the former with a planar Li 2 N 2 ring, the latter possessing an N−Li−N−Li chain structure. Triply metallated trianilinoborane (15) crystallized as dimeric B(NLiPh) 3 ·LiCl·(OEt 2 ) 3 (15A). Treatment of trianilino-

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Section: Tris(2-pyridylamino)borane (4)mentioning

confidence: 99%

Section: H 14 Li·pmdetamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Triaminoboranes and Their Metallation toN-Lithiotriaminoboranes

Braun¹,

Habereder²,

Nöth³

et al. 2002

Eur. J. Inorg. Chem.

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“…Neue Mo È glichkeiten ero È ffneten Umsetzungen dimetallierter Bis(alkylamino)phenylborane mit ECl 4 und EX 2 Me 2 (E = Sn, Ge; X = Cl, Br) [3,4]. In allen Fa È llen waren sterisch anspruchsvolle Substituenten am Stickstoff erforderlich, um einerseits die Bildung viergliedriger Ringe zu erzwingen und andererseits die Reaktivita È t der Metallacyc-len herabzusetzen.…”

Section: Introductionunclassified

“…Deshalb haben wir zuna È chst den 2,4,6-Triisopropylphenylrest gewa È hlt, u È ber dessen Einfluû auf Ringgro Èûe und -eigenschaften in dieser Arbeit berichtet wird. Bei der Umsetzung dimetallierter Bis(alkylamino)phenylborane mit Tetrahalogeniden des Germaniums, Zinns und Titans gelangt man zu spirocyclischen Verbindungen mit dem jeweiligen Metallatom im Zentrum [3]. So lieûen sich auch hier die beschriebenen Bis(alkylamino)-(2,4,6-triisopropylphenyl)borane II c und II d nach ihrer Dilithiierung mit Germaniumbzw.…”

Section: Introductionunclassified