ChemInform Abstract: PREPARATION, REACTIONS, AND STRUCTURE OF TERT‐BUTYL(TERT‐BUTYLIMINO)BORANE

Paetzold, Peter; Plotho, C. Von; Schmid, Günter; Boese, Roland; Schräder, Bernhard; Bougeard, D.; Pfeiffer, U.; Gleiter, Rolf; Schaefer, W.

doi:10.1002/chin.198423251

Cited by 4 publications

(7 citation statements)

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“…Consistently, in compound VIII the B–N distance amounts to 1.588(3) Å 11. An extremely long B–N bond was found in the Dewar borazine IX [1.752 Å] 12…”

Section: Resultsmentioning

confidence: 66%

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

et al. 2006

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Oxidation of the 1,3,2‐diazaborole tBuNaCH=CHNb(tBu)BBr(Na–B) (1h) with NO+PF6– afforded the diazaborolium salts [tBuNa=CH–CH=Nb(tBu)BF2(Na–B)]+X– (X = Br–, Br3–, PF6–) (3h) as the result of different oxidation processes. The same product was obtained when the 1,3,2‐diazaborolidine tBuNaCH2CH2Nb(tBu)BBr(Na–B) (2h) was subjected to reaction with NO+PF6–. In contrast to this, oxidation of 1h and 2h with NO+BF4– cleanly furnished [tBuNaCH–CH=Nb(tBu)BFBr(Na–B)]+BF4– (6h). Treatment of the 1,3,2‐diazaboroles tBuNaCH=CHNb(tBu)BR(Na–B) [R = H (1e), CN (1i), C≡CH (1j)] with NO+PF6– under comparable conditions led to the borolium salts [tBuNa=CH–CH=Nb(tBu)BRF(Na–B)]+PF6– [R = H (3e), CN (3i), C≡CH (3j)]. All the borolium salts investigated in this study were reversibly reduced by cyclic voltammetry. The novel products were characterized by elemental analyses and NMR spectra (1H, 11B, 13C, 19F, 31P). The X‐ray structure analysis of 3h reveals two independent planar cations in the asymmetric unit, accompanied by one bromide and one tribromide ion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…Consistently, in compound VIII the B–N distance amounts to 1.588(3) Å 11. An extremely long B–N bond was found in the Dewar borazine IX [1.752 Å] 12…”

Section: Resultsmentioning

confidence: 66%

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

et al. 2006

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“…The B1–N1 bond distance for 2 [1.341(3) Å] is significantly shorter than that in 1 [1.405(8) Å] but comparable to those for BN bonds of II – IV (1.304–1.340 Å). Nevertheless, it is substantially longer than the BN bond distances in typical iminoborane species without Lewis base coordination (∼1.25 Å), which is ascribed to the electron shift from π bonding to a nitrogen atom of 2 induced by NHC coordination. Likewise, different from the essentially linear iminoboranes with formal sp-hybridized boron and nitrogen atoms, the C1–N1–B1 and N1–B1–O1 bond angles in 2 twist to be 140.54(19)° and 125.9(2)°, respectively.…”

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confidence: 89%

“…Compared with isoelectronic alkynes, iminoboranes exhibit much higher reactivity because of their strong polarity and the relative weakness of their BN triple bonds . Indeed, the transient iminoboranes are liable to cyclooligomerize, whereas these isolable counterparts spontaneously cyclize with polar unsaturated bonds through [2 + 2] and [2 + 3] cycloaddition manners . In the presence of a ruthenium catalyst, the cyclization between iminoborane t BuBN t Bu and nonpolar alkynes proceeds smoothly to afford 1,2-azaborinine and 1,4-azaborinine derivatives .…”

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confidence: 99%

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species

et al. 2020

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The synthesis, characterization, and reactivity of an iminoborane–N-heterocyclic carbene (NHC) adduct were described. The reaction of DmpNHB(OEt)Br [1; Dmp = 2,6-bis(2,4,6-trimethylphenyl)phenyl] with 2 equiv of 1,3-diimethyl-4,5-dimethylimidazol-2-ylidene (IMe4) resulted in the formation of an iminoborane–NHC complex 2. Both X-ray analysis and density functional theory calculations revealed the double-bond character of the BN bond in 2. Interestingly, compared with the corresponding Lewis-base-free iminoborane, 2 features a nitrogen atom with increased electron density, which could be attributed to coordination of the NHC. Similar to the isoelectronic species imine, this nitrogen center in 2 can be easily attacked by electrophiles. Indeed, the reaction of 2 with trimethylsilyl triflate (Me3SiOTf) afforded an NHC-stabilized borenium cation 3, representing a facile strategy to prepare cationic tricoordinate boron species.

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“…These (RBNR) 2 dimers can be isolated in the presence of bulky substituents R, in analogy to the known 1,3-dioxa-2,4-diboretanes 7 bearing large groups. ,, The presence of trimers resembling Dewar benzene, established in the RBNR series, , is not observed here. Indeed, the attempted geometry optimization of a Dewar boroxole resulted in 3b instead.…”

Section: Resultsmentioning

confidence: 62%

Reversible Formation of Organyl(oxo)boranes (RBO) (R = C₆H₅or CH₃) from Boroxins ((RBO)₃): A Matrix Isolation Study

Bettinger

2007

Organometallics

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Flash vacuum pyrolysis of triphenyl- and trimethylboroxin and subsequent trapping of the gas phase products in a large excess of argon at T < 20 K allows matrix isolation and characterization by IR spectroscopy of phenyl(oxo)borane and methyl(oxo)borane. The nature of the matrix isolated species, monomeric CH3BO, 1:1 dimer complex of CH3BO, (CH3BO)2, and (CH3BO)3, depends strongly on the trapping temperature and matrix host gas (Ar vs Xe) with the boroxin dominating at 30 K (Ar) or 55 K (Xe). An ab initio investigation (second-order Møller−Plesset perturbation theory) of the potential energy surface for trimerization of CH3BO is in agreement with the experimental observations.

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ChemInform Abstract: PREPARATION, REACTIONS, AND STRUCTURE OF TERT‐BUTYL(TERT‐BUTYLIMINO)BORANE

Abstract: Das aus dem Amin (I) und dem Boran (II) dargestellte Aminoboran (III) läßt sich thermisch unter Bildung der Titelverbindung (IV) (Röntgenstrukturanalyse: Pnma; Z=4), einer farblosen Flüssigkeit, zersetzen.

Cited by 4 publications

References 1 publication

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species

Reversible Formation of Organyl(oxo)boranes (RBO) (R = C₆H₅or CH₃) from Boroxins ((RBO)₃): A Matrix Isolation Study

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ChemInform Abstract: PREPARATION, REACTIONS, AND STRUCTURE OF TERT‐BUTYL(TERT‐BUTYLIMINO)BORANE

Abstract: Das aus dem Amin (I) und dem Boran (II) dargestellte Aminoboran (III) läßt sich thermisch unter Bildung der Titelverbindung (IV) (Röntgenstrukturanalyse: Pnma; Z=4), einer farblosen Flüssigkeit, zersetzen.

Cited by 4 publications

References 1 publication

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

Chemical Oxidation of 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidines

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species

Reversible Formation of Organyl(oxo)boranes (RBO) (R = C6H5or CH3) from Boroxins ((RBO)3): A Matrix Isolation Study

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Reversible Formation of Organyl(oxo)boranes (RBO) (R = C₆H₅or CH₃) from Boroxins ((RBO)₃): A Matrix Isolation Study