Reaktionen der Azadiboriridine: Clusterbildung und Ringerweiterung

Paetzold, Peter; Redenz‐Stormanns, Burkhard; Boese, Roland

doi:10.1002/cber.19911241111

Cited by 27 publications

(20 citation statements)

References 19 publications

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“…With a cyclic diborane(4) like 1 a, the reactivity towards multiple bonds may be enhanced by ring tension, but may also be lowered by the bulky tBu ligands. Actually, 1 a reacts spontaneously with 3-hexyne [12] and also with the iminoborane EtBºNtBu [12]. We report here on the reaction of 1 a with a series of alkenes.…”

Section: Addition Of Pivalic Acid To 1 Amentioning

confidence: 99%

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Reactions at the B-B Bond of Tri-tert-butylazadiboriridine NB2R3: Ring Extensions

Luckert¹,

Eversheim²,

Englert³

et al. 2001

Z. anorg. allg. Chem.

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The OCO carboxylate unit of pivalic acid adds to the B±B bond of the azadiboriridine NB 2 R 3 (1 a, R = tBu) to give the chiral heterocyclohexadiene 2 a; the enantiomers of 2 a are transformed into one another by a [1,3] sigmatropic hydride transfer along the B±N±B ring fragment. The azadiboracyclopentanes 3 a±e are formed from 1 a and the alkenes ethene, propene, isobutene, (trimethylsilyl)ethene, and 2,3-dimethyl-1-butene. Only one double bond of cyclopentadiene and 1,3-butadiene reacts in the same way to give 3 f, g, respectively, and both of the double bonds of 1,3-butadiene react with an excess of 1 a to give 3 h, which is obtained in a 9 : 1 mixture of racemate and meso-isomer; the meso-isomer crystallizes in the space group P2 1 /n. The corresponding diazadiboracyclopentane 3 i and the triazadiboracyclopentane 3 j are formed from 1 a and N-phenyl benzaldimine or azobenzene, respectively. Ethyne and 1 a give either the azadiboracyclopentene 4 a (1 : 1) or the diazatetraborabicyclo-[3.3.0]octane 3 k (1 : 2). The phosphaalkyne PºC±tBu and 1 a analogously yield the heterocyclopentene 4 c. The insertion of SitBu 2 into 1 a to give the azasiladiboracyclobutane 5 a is achieved by applying Li powder and tBu 2 SiCl 2 . The hitherto unknown azadiboriridines BN 2 R 2 R' (R = tBu; R' = 1-iPr, 2-Mes, 2-CMe 2 Et: 1 b±d) were synthesized by the chloroboration of the iminoboranes RBºNiPr and RBºNR with RBCl 2 , MesBCl 2 , and (EtMe 2 C)BCl 2 , respectively, and subsequent dechlorination of the isolated and characterized diborylamines Cl±BR±NiPr±BR±Cl (6 a), Cl±BR±NR± BMes±Cl (6 b), and Cl±BR±NR±B(CMe 2 Et)±Cl (6 c), respectively, with lithium (Mes = mesityl).The azadiboriridine 1 b dimerizes to give the diaza-nido-hexaborane 7 a, whereas 1 c and 1 d are storable at room temperature. The product 1 c crystallizes as a racemate in the space group P2 1 /c; its ring geometry differs from that of the known N-mesityl isomer.Reaktionen an der B±B-Bindung von Tri-tert-butylazadiboriridin NB 2 R 3 : Ringererweiterungen Inhaltsu È bersicht. Die OCO-Carboxylateinheit der Privalinsa È ure addiert sich an die B±B-Bindung des Azadiboriridins NB 2 R 3 (1 a, R = tBu) unter Bildung des chiralen Heterocyclohexadiens 2 a; die Enantiomeren von 2 a gehen durch [1,3]-sigmatropen Hydridtransfer entlang dem B±N±B-Ringfragment ineinander u È ber. Die Azaboracyclopentane 3 a±e entstehen aus 1 a und den Alkenen Ethen, Propen, Isobuten, (Trimethylsilyl)ethen bzw. 2,3-Dimethyl-1-buten. Je eine Doppelbindung von Cyclopentadien und 1,3-Butadien ergibt mit 1 a die Azadiboracyclopentane 3 f, g, und beide Doppelbindungen von 1,3-Butadien reagieren mit 1 a im Verha È ltnis 1 : 2 zu 3 h ab, das als 9 : 1-Mischung aus Racemat und mesoForm anfa È llt; das meso-Isomer kristallisiert in der Raumgruppe P2 1 /n. N-Phenylbenzaldimin und Azobenzol bilden mit 1 a das Diazadiboracyclopentan 3 i bzw. das Triazadiboracyclopentan 3 j. Die 1 : 1-Reaktion von 1 a und Ethin erbringt das Azadiboracyclopenten 4 a und die 2 : 1-Reaktion das Diazatetraborabicyclo[3.3.0]octan 3 ...

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Section: Addition Of Pivalic Acid To 1 Amentioning

confidence: 99%

“…As expected for diborane-4 derivatives, the B±B bond of 1 a adds to 3-hexyne to give the (3 + 2) cycloadduct H [12]. Certain polar reagents A±X open 1 a, when X promises some B=X p-interaction in the products of type I (A±X = H±OMe etc.)…”

Section: Introductionmentioning

confidence: 99%

Reactions at the B-B Bond of Tri-tert-butylazadiboriridine NB2R3: Ring Extensions

Luckert¹,

Eversheim²,

Englert³

et al. 2001

Z. anorg. allg. Chem.

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“…The 11-tively [37] . vertex nido species [NB 10 2 HRh [43] , (C 6 Me 6 )Ru, (Ph 3 P) 2 Ni [44] ; Eqs. The nido cluster NB 9 H 12 (14) is sensitive towards protic (5), (6) Ϫ (45; M ϭ Co [44] ).…”

mentioning

confidence: 99%

“…9 hypho NB 8 13 [17] 10 nido NB 9 NB 8 M 14 [13] [18] [19] [20] [21] [22] 15 [23] 16 [23] 17 [24] 10 arachno NB 9 N 2 B 8 NCB 8 SNB 8 NB 8 M 18 [21] [25] [26] 19 [25] 20 [27] 21 [28] 22 [12] 23 [24] 11 arachno NB 10 [30] 11 hypho SNB 9 S 2 NCB 7 28 [30] 29 [34] 12 nido NB 11 30 [35] 31…”

mentioning

confidence: 99%

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Five- and Six-Coordinate Nitrogen in Azaborane Clusters

Paetzold¹

1998

Eur. J. Inorg. Chem.

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In the majority of known azaboranes NaBbHc and their derivatives, the coordination number of the nitrogen atoms within the cluster does not exceed the classical values of 3 or 4. In the azaboranes closo‐NB9H10, nido‐NB10H13, and closo‐NB11H12 and in their derivatives, however, the nitrogen atoms are 5‐ or 6‐coordinate and thus represent a novel bonding situation. The synthesis, structure, and reactivity of these azaboranes are reviewed in this article.

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Five- and Six-Coordinate Nitrogen in Azaborane Clusters

Paetzold

1998

Eur. J. Inorg. Chem.

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In the majority of known azaboranes N a B b H c and their deriv-NB 11 H 12 and in their derivatives, however, the nitrogen atoms are 5-or 6-coordinate and thus represent a novel bon-atives, the coordination number of the nitrogen atoms within the cluster does not exceed the classical values of 3 or 4. In ding situation. The synthesis, structure, and reactivity of these azaboranes are reviewed in this article. the azaboranes closo-NB 9 H 10 , nido-NB 10 H 13 , and closo- Peter Paetzold, born in 1935, received his doctoral degree on his workMICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included.

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Reaktionen der Azadiboriridine: Clusterbildung und Ringerweiterung

Cited by 27 publications

References 19 publications

Reactions at the B-B Bond of Tri-tert-butylazadiboriridine NB2R3: Ring Extensions

Reactions at the B-B Bond of Tri-tert-butylazadiboriridine NB2R3: Ring Extensions

Five- and Six-Coordinate Nitrogen in Azaborane Clusters

Five- and Six-Coordinate Nitrogen in Azaborane Clusters

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