<i>arachno</i>‐Diazapentaboranes

Küpper, Stefan; Englert, U.; Paetzold, Peter

doi:10.1002/hc.520010609

Cited by 8 publications

(8 citation statements)

References 18 publications

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“…The addition of the alcohols iPrOH and tBuOH and of the amine iPr 2 NH to MeBϭCA 2 proceeds in a straight-forward way, according to eqs. The structure of the products was identified by characteristic 1 H, 11 B, and 13 C NMR shifts, the intensity of the 1 H NMR signals and the expected NMR coupling schemes ( Table 2). One set of signals was observed for the alkoxyboranes 2a, b.…”

Section: Addition Of Protic Agentsmentioning

confidence: 99%

“…A comparable product (2eЈ) had been formed by the addition of BH 3 (thf) to the diazadiboretane (RBNtBu) 2 , according to Eq. (2dЈ) [11]. Typical for the structure of 2e are two IR bands at ν ϭ 2455 and 1533 cm Ϫ1 , representing vibrations of the terminal and the bridging hydrogen atoms.…”

Section: Addition Of Hydridic Agentsmentioning

confidence: 99%

“…Finally, the nitrone OϪNMeϭCHPh and MeBϭCA 2 or MeBϭCAAЈ give the corresponding (2ϩ3) cycloadducts 5e, f, respectively. All of the products were characterized by their 1 H, 11…”

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Reactions at the Boron‐Carbon Double Bond of Methyl(methylidene)boranes

Paetzold¹,

Englert²,

Finger³

et al. 2004

Zeitschrift anorg allge chemie

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The addition of Lewis bases L to the methyl(methylidene)boranes MeBϭCA 2 (A ϭ SiMe 3 ) and MeBϭCAAЈ (AЈ ϭ SiMe 2 Cl) gives the adducts MeB(L)ϭCA 2 (1a, b; L ϭ trimethylpyridine, PMe 3 ) and MeB(L)ϭCAAЈ (1c, d; L ϭ di-and trimethylpyridine), respectively. Alcohols and amines HX are added to the BC double bond to give boranes MeB(X)ϪCHA 2 (8aϪc; X ϭ OiPr, OtBu, NiPr 2 ); MeBϭCAAЈ and HNMe 2 react in the ratio 1:2, yielding MeB(X)ϪCHA(SiMe 2 X) (2d; X ϭ NMe 2 ). From MeBϭCA 2 and BH 3 , the five-membered ring [ϪCA 2 ϪBHϪCA 2 ϪBMe(Hm) 2 BMeϪ] (2e; 2:1) or the six-membered ring [ϪCA 2 ϪBH(H µ ) 2 BMeϪCA 2 ϪBH(H µ ) 2 BMeϪ] (2f; 1:1) are formed, both containing double hydrogen bridges; the product 2f crystallizes in the space group P1. The metallocene trihydrides [Cp 2 MH 3 ] add to the BC double bond under formation of a double hydrogen bridge to give [Me(A 2 CH)B(H µ ) 2 MCp 2 ] (2g, h; M ϭ Nb, Ta). MeBϭCA 2 can be chloroborated, -stannated, and -phosphated with EϪCl to yield the boryldisilylmethanes MeB(Cl)ϪCA 2 ϪE (2iϪl; E ϭ EtClB, tBuClB, Me 2 ClSn, Cl 2 P). The alkyloboration and -alumination with EϪR leads to the boryldisilylmethanes MeBRϪSiA 2 ϪE (2mϪo; EϪR ϭ Me 2 BϪMe, Et 2 BϪEt, Cl 2 AlϪEt) and the bromination to MeB(Br)ϪCA 2 Br. (2ϩ2) Cycloadditions are achieved, when MeBϭCA 2 is reacted with unsaturated molecules aϭb, yielding four-membered rings [ϪBMeϪCA 2 ϪbϪaϪ] [4aϪd; aϭb ϭ fluorenone, bis(methoxycarbonyl)ethyne (reacting at both of the CϭO bonds), phenylisocyan-Reaktionen an der Bor-Kohlenstoff-Doppelbindung von Methyl(methyliden)boranen Inhaltsübersicht. Die Addition von Lewisbasen L an die Methyl-(methyliden)borane MeBϭCA 2 (A ϭ SiMe 3 ) und MeBϭCAAЈ (AЈ ϭ SiMe 2 Cl) führt zu den Addukten MeB(L)ϭCA 2 (1a, b; L ϭ Trimethylpyridin, PMe 3 ) bzw. MeB(L)ϭCAAЈ (1c,d; L ϭ Di-und Trimethylpyridin). Alkohole und Amine HX addieren sich an die BC-Doppelbindung unter Bildung von MeB(X)ϪCHA 2 (2a-c; X ϭ OiPr, OtBu, NiPr 2 ); MeBϭCAAЈ und HNMe 2 reagieren im Verhältnis 1:2 zu MeB(X)ϪCHA(SiMe 2 X) (2d; X ϭ NMe 2 ). Aus MeBϭCA 2 und BH 3 bilden sich der fünfgliedrige Ring [ϪCA 2 ϪBHϪCA 2 ϪBMe(H µ ) 2 BMeϪ] (2e; 1:2) oder der sechsgliedrige Ring [ϪCA 2 ϪBH(H µ ) 2 BMeϪCA 2 ϪBH(H µ ) 2 BMeϪ] (2f; 1:1), die beide Wasserstoff-Doppelbrücken enthalten; der Sechsring 2f kristallisiert in der Raumgruppe P1. Die Metallocentrihydride [Cp 2 MH 3 ] addieren sich an die BC-Doppelbindung unter Bildung einer Wasserstoff-Doppelbrücke zu [Me(A 2 CH)B(H µ ) 2 MCp 2 ] (2g, h; M ϭ Hf, Ta). MeBϭCA 2 kann mit EϪCl zu Boryldisilylmethanen MeB(Cl)ϪCA 2 ϪE chloroboriert, -stanniert und -phosphaniert werden (2iϪl; E ϭ EtClB, tBuClB, Me 2 ClSn, Cl 2 P). Die Alkyloborierung und -aluminierung mit EϪR ergibt die Boryldisilylmethane MeB(R)ϪCA 2 ϪE (2mϪo; EϪR ϭ Me 2 BϪMe, Et 2 BϪEt, Cl 2 AlϪEt) und die Bromierung MeB(Br)ϪCA 2 Br (2p). (2ϩ2)-Cycloadditionen beobachtet man, wenn MeBϭCA 2 mit ungesättigten Molekülen aϭb zu Vierringen [ϪBMeϪCA 2 ϪbϪaϪ] [4aϪd;508 MeBϭCAAЈ und AN 3 . Schließlich entstehen aus MeBϭCA 2 bzw.MeBBϭCAAЈ und dem Nitron OϪNMeϭC...

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Section: Addition Of Protic Agentsmentioning

confidence: 99%

Section: Addition Of Hydridic Agentsmentioning

confidence: 99%

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Reactions at the Boron‐Carbon Double Bond of Methyl(methylidene)boranes

Paetzold¹,

Englert²,

Finger³

et al. 2004

Zeitschrift anorg allge chemie

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“…Vertices Type Skeletal atoms Number in Figure 2 4 nido NB 3 1 [5] [6] 2 [6] 5 arachno N 2 B 3 SNB 3 3 [6] 4 [7] 5 [8] 6 nido N 2 B 4 6 [9] [10] 8 arachno N 2 B 6 7 [11] 8 hypho SNB 6 8 [12] 9 nido NB 8 NB 7 M 9 [13] 10 [14] 9…”

Section: Introductionmentioning

confidence: 99%

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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“…Azaboranes and azaheteroboranes with a nitrogen connectivity of 2 or 3 (read BR instead of BH in 1؊6) Table 2. Azaboranes and azaheteroboranes with nitrogen connectivity of 2 or 3 Vertices Type Skeletal atoms Number in Figure 2 4 nido NB 3 1 [5] [6] 2 [6] 5 arachno N 2 B 3 SNB 3 3 [6] 4 [7] 5 [8] 6 nido N 2 B 4 6…”

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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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arachno‐Diazapentaboranes

Cited by 8 publications

References 18 publications

Reactions at the Boron‐Carbon Double Bond of Methyl(methylidene)boranes

Reactions at the Boron‐Carbon Double Bond of Methyl(methylidene)boranes

Five- and Six-Coordinate Nitrogen in Azaborane Clusters

Five- and Six-Coordinate Nitrogen in Azaborane Clusters

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