1,1,1-Trisborylalkanes as Precursors for Dicarbapentaboranes(5) − Synthesis, Reactivity, and Structures ofcloso-1,5-Bis(neopentyl)-2,3,4-trichloro-1,5-dicarbapentaborane and Its Derivatives

Bayer, Michael J.; Pritzkow, Hans; Siebert, Walter

doi:10.1002/1099-0682(200206)2002:6<1293::aid-ejic1293>3.0.co;2-2

Cited by 30 publications

(7 citation statements)

References 24 publications

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“…Aus den Rechnungen und dem chemischen Verhalten der Carbaalane folgern wir, dass die Koordination zum Lithium die [ t BuCH 2 C(AlH 2 ⋅NMe 3 ) 3 ]‐Einheit stabilisiert und die Kondensation zu einem Cluster verhindert. In der Borchemie ist die analoge Verbindung t BuCH 2 C(BCl 2 ) 3 bekannt 7. Verbindungen dieses Typs werden durch Hydroborierung von t BuCCBCl 2 mit in situ hergestelltem HBCl 2 gewonnen und können nachfolgend in closo ‐C 2 B 3 ‐Carbaborane überführt werden.…”

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Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

Stasch¹,

Roesky²,

Schleyer³

et al. 2003

Angewandte Chemie

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Das erste Carbaalanat besteht aus einem Carbaalan‐Dianion, [(AlH)8(CCH2tBu)6]2−, das über Hydridbrücken an zwei Lithiumionen auf gegenüberliegenden Seiten des Clusters angeordnet ist (siehe Abbildung). Zusätzlich sind die Lithiumionen jeweils an eine neutrale [tBuCH2C(AlH2⋅NMe3)3]‐Einheit koordiniert. In dieser Anordnung verhindert das Lithiumion die Kondensation der [tBuCH2C(AlH2⋅NMe3)3]‐Einheiten.

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unclassified

Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

Stasch¹,

Roesky²,

Schleyer³

et al. 2003

Angewandte Chemie

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“…1, different BÐO bond lengths are observed. The BÐO distances between atom O1 and the sp 2 -hybridized atoms B1 and B2 [1.353 (2) and 1.363 (2) A Ê , respectively] lie in the range of comparable BÐO bond lengths found in catecholborylalkanes, C 6 H 4 O 2 BR (BÐO = 1.39 A Ê ; Bayer et al, 2002), and in oxadiboroles [BÐO = 1.374 (3) A Ê ; Ko È ster et al, 1994]. The B2ÐO2, B1ÐO3, B6ÐO4 and B8ÐO5 bond lengths in (II) are elongated [1.414 (2)±1.433 (2) A Ê ] because of the threefold coordination of the O atoms.…”

Section: Commentmentioning

confidence: 89%

A `tetrameric' 3,4-di-p-tolyl-1,2,5-oxadiborole derivative

2003

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In the title compound, 1,1,6a,7,9a,10-hexachloro-2,3,5,6,8,9,11,12-octa-p-tolyl-1,6a,9a,12a-tetraborata-3a,4a,7,10-tetrabora-4a(1),6b,9b,12b-tetraoxonia-4-oxatetracyclopenta[1,2-a:2,1,5-de:1,2-g:1,2-i]naphthalene dichloromethane pentasolvate, C(64)H(56)B(8)Cl(6)O(5).5CH(2)Cl(2), two condensed oxadiborole rings are attached to two further oxadiborole rings in a type of donor-acceptor bonding, thus forming a ten-membered alternating (B-O)(5) naphthalene-like arrangement as the central building block.

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“…For the synthesis of 9a, the tris(dichloroboryl)neopentylmethane (18a) is needed [13]. It is obtained via lithiation of 3,3-dimethyl-1-butyne, followed by boron/lithium exchange to give the intermediate Me 3 C-C≡C-BCl 2 , which then is hydroborated with HBCl 2 prepared in situ.…”

Section: Closo-and Nido-carboranesmentioning

confidence: 99%

“…The 11 B NMR signal of 9b is shifted to δ = 17.3. Further replacements of the chloro substituents of 9a were possible with Me 3 CC 2 Li, PhC 2 Li, and Me 3 SiNMe 2 to give the tris(acetylenic) derivatives 9c and 9d, as well as the trisamino compound 9e [13].…”

Section: W Siebert Et Almentioning

confidence: 99%

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Small boranes, carboranes, and heterocarboranes

Siebert

Maier

et al. 2003

Pure and Applied Chemistry

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Dehalogenation of 1,2-dichloro-diborane(4) derivatives with Na/K alloy does not lead to planar cyclo-tetraboranes but to the blue puckered diisopropylamino compound and to the yellow 2,2,6,6-tetramethylpiperidino-tetraboratetrahedrane derivative, respectively. With smaller dialkylamino substituents, the formation of orange-red cyclo-hexaborane (BNMe 2 ) 6 and the green closo-hexaborane (BNEt 2 ) 6 is observed. When a 1:1 mixture of Me 2 NBCl 2 and [Me 2 N(Cl)B] 2 is dehalogenated, a small amount of colorless crystals of the planar diamond-shaped tetrabora-bicyclo-butane [(Me 2 N) 2 BB−BNMe 2 ] 2 is obtained. Its MO analysis reveals that eight framework electrons are used to form two 3c,2e σ bonds, one 4c,2e π bond, and one 4c,2e σ bond along the edges.A new approach to reactive closo-dicarbapentaboranes involves the hydroboration of dichloroboryl-tbutylacetylene with HBCl 2 leading to Me 3 CCH 2 C(BCl 2 ) 3 . On heating, it is transformed into the closo-dicarbapentaborane (Me 3 CCH 2 C) 2 (BCl) 3 , in which the chlorine atoms may be substituted to give new derivatives.By reacting B 2 Cl 4 with C 5 Me 5 -SiMe 3 the nido-1-borane-2,3,4,5,6-pentacarbahexaborane(6) is stabilized by the Lewis acid BCl 3 to give (MeC) 5 B−BCl 3 .Hydroboration of 3,4-bis(isopropylidene)-1,3-diborolanes leads to the formation of nido-2,3,5-tricarbahexaboranes(7), which may be deprotonated to give the corresponding anions isolobal with C 5 H 5 − . Heterotricarbahexaboranes are obtained when a 3,4-bis(dichloroboryl)-2,5-hexadiene derivative is reacted with heptamethyldisilazane and hexamethyl-disilthiane to give the corresponding 1,2,5-azadiborolane and thiadiborolane. Their hydroboration leads to the aza-and thia-nido-dicarbahexaboranes, respectively.

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1,1,1-Trisborylalkanes as Precursors for Dicarbapentaboranes(5) − Synthesis, Reactivity, and Structures ofcloso-1,5-Bis(neopentyl)-2,3,4-trichloro-1,5-dicarbapentaborane and Its Derivatives

Cited by 30 publications

References 24 publications

Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

A `tetrameric' 3,4-di-p-tolyl-1,2,5-oxadiborole derivative

Small boranes, carboranes, and heterocarboranes

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1,1,1-Trisborylalkanes as Precursors for Dicarbapentaboranes(5) − Synthesis, Reactivity, and Structures ofcloso-1,5-Bis(neopentyl)-2,3,4-trichloro-1,5-dicarbapentaborane and Its Derivatives

Cited by 30 publications

References 24 publications

Ein dreifach AlH2‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

Ein dreifach AlH2‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

A `tetrameric' 3,4-di-p-tolyl-1,2,5-oxadiborole derivative

Small boranes, carboranes, and heterocarboranes

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Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats

Ein dreifach AlH₂‐koordiniertes Kohlenstoffatom als Teil eines Carbaalanats