9,10‐Dihydro‐9,10‐diboraanthracene: Supramolecular Structure and Use as a Building Block for Luminescent Conjugated Polymers

Lorbach, Andreas; Bolte, Michael; Li, Haiyan; Lerner, Hans‐Wolfram; Holthausen, Max C.; Jäkle, Frieder; Wagner, Mat­thias

doi:10.1002/ange.200901226

Cited by 77 publications

(24 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The dimer is held together by two central B-H-B two-electron-three-center bonds. The resulting interdimer B2···B2# distance is 1.817 (2) , which compares well with the respective intermonomer B···B distances in polymeric DBA ((DBA) n ; Figure 3, bottom; average value: 1.818(12) [64] ). Furthermore, similar to (DBA) n , the monomeric units of compound (7) 2 deviate significantly from planarity with a dihedral angle of 135.88 between the two phenylene rings (cf.…”

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh supporting

confidence: 63%

“…It has been suggested that monomer-folding in (DBA) n is the result of otherwise-unfavorable steric interactions between adjacent DBA moieties and the same reasoning is probably true for compound (7) 2 . [64,65] Compound (7) 2 features B1 À S1 bond lengths of 1.997 (1) , which are somewhat shorter than in the corresponding syn-diadduct of DBA, that is,…”

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh mentioning

confidence: 97%

“…The supernatant gave characteristic NMR spectra of ( [62] and the precipitate was identified as (DBA) n . [64] This result leads to the conclusion that, upon dissolution, compound (7) 2 undergoes a redistribution of its SMe 2 ligands so that two of them are attached to the same DBA molecule, whilst the other molecule stabilizes itself by polymerization through B-H-B two-electron-three-center bonds.…”

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh mentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, Coupling, and Condensation Reactions of 1,2‐Diborylated Benzenes: An Experimental and Quantum‐Chemical Study

Seven

Zhu

et al. 2012

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

1,2-Bis(pinacolboryl)benzene (1,2-C(6)H(4) (Bpin)(2), 2) was synthesized in preparatively useful yields from 1,2-C(6)H(4)Br(2), iPrO-Bpin, and Mg turnings in the presence of 1,2-C(2)H(4)Br(2) as an entrainer. Compound 2 is a versatile starting material for the synthesis of (un)symmetrically substituted benzenes (i.e., 1,2-C(6)H(4)(Ar(1))(Ar(2))) through sequential Suzuki-Miyaura coupling reactions. Alternatively, it can be transformed into bis-borate Li(2)[1,2-C(6)H(4)(BH(3))(2)] (3) through reduction with Li[AlH(4)]. In the crystal lattice, the diethyl ether solvate 3·OEt(2) establishes a columnar structure that is reinforced by an intricate network of B-(μ-H)-Li interactions. Hydride-abstraction from compound 3 with Me(3)SiCl leads to the transient ditopic borane 1,2-C(6)H(4)(BH(2))(2), which can either be used in situ for subsequent hydroboration reactions or trapped as its stable NMe(2)Et diadduct (6). In SMe(2) solution, the putative diadduct 1,2-C(6)H(4)(BH(2)·SMe(2))(2) is not long-term stable but rather undergoes a condensation reaction to give 9,10-dihydro-9,10-diboraanthracene, HB(μ-C(6)H(4))(2)BH, and BH(3). 9,10-Dihydro-9,10-diboraanthracene was isolated from the reaction mixture as its SMe(2) monoadduct (7), which dimerizes in the solid state through two B-H-B bridges ((7)(2), elucidated by X-ray crystallography). In contrast, hydride-abstraction from compound 3 in THF or CH(2)Cl(2) provides the unique exo-adduct H(2)B(μ-H)(2)B(μ-C(6)H(4))(2)B(μ-H)(2)BH(2) (8, elucidated by X-ray crystallography). Quantum-chemical calculations on various conceivable isomers of [1,2-C(6)H(4)(BH(2))(2)](2) revealed that compound 8 was the most stable of these species. Moreover, the calculations confirmed the experimental findings that the NMe(2)Et diadduct of 1,2-C(6)H(4)(BH(2))(2) is significantly more stable than the corresponding SMe(2) complex and that the latter complex is not able to compete successfully with borane-dimerization and -condensation. The reaction cascade in SMe(2), which proceeds from 1,2-C(6)H(4)(BH(2))(2) to the observed adducts of HB(μ-C(6)H(4))(2)BH, has been elucidated in detail and the important role of B-C-B-bridged intermediates has been firmly established.

show abstract

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh supporting

confidence: 63%

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh mentioning

confidence: 97%

Section: Reactivity Of 12-c 6 H 4 a C H T U N G T R E N N U N G (Bh mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Coupling, and Condensation Reactions of 1,2‐Diborylated Benzenes: An Experimental and Quantum‐Chemical Study

Seven

Zhu

et al. 2012

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Das 9,10‐Dihydro‐9,10‐diboranthracen (28) zeigt im Festkörper eine supramolekulare Struktur über Hydridbrücken analog zum Diboran. Hydroborierung mit geeigneten Diethinylbenzolen liefert grünlumineszierende konjugierte Polymere (29) 1_65…”

Section: Konjugierte Materialienunclassified

Anorganische Chemie 2009

Baumgartner¹,

Pietschnig²,

Schatzschneider³

et al. 2010

Nachr Chem

View full text Add to dashboard Cite

Molekülchemie der Hauptgruppenelemente: Trends wie die Donorstabilisierung niedervalenter Zentren oder allgemein Donor‐Akzeptor‐Synergien wurden weiter entwickelt. Bioanorganik: Neben den Forschungsfeldern der Metalloenzyme und des Metalloprotein‐Engineerings war die medizinische anorganische Chemie sehr dynamisch. Koordinationschemie: Artifizielle Systeme, die Methan in Methanol umwandeln, stehen möglicherweise am Beginn einer rasanten Entwicklung.

show abstract

“…Compound 1 is the key starting material for the synthesis of (i) (phenyl) [2-(trimethylsilyl)phenyl]iodonium triflate (A; Scheme 1), one of the most efficient benzyne precursors available to date, [4,5] (ii) 9,10-dihydro-9,10-diboraanthracene (B; Scheme 1), a versatile building block of luminescent boron-doped p-conjugated polymers, [6,7] and (iii) 9,10-dimethyl-9,10-dihydro-9,10-diboraanthracene, a powerful ditopic LewisScheme 1. 1,2-Bis(trimethylsilyl)benzene (1) is a key starting material for the preparation of the benzyne precursor A, the polymer building block B, and Lewis-acid catalysts C. (i) cf.…”

Section: Introductionmentioning

confidence: 99%

Improved Synthesis of 1,2‐Bis(trimethylsilyl)benzenes using Rieke‐Magnesium or the Entrainment Method

Lorbach¹,

Reus²,

Bolte³

et al. 2010

Adv Synth Catal

Self Cite

View full text Add to dashboard Cite

1,2-Bis(trimethylsilyl)benzene is the key starting material for the synthesis of efficient benzyne precursors and certain luminescent p-conjugated materials. We now report that it can be conveniently prepared in tetrahydrofuran from 1,2-dibromobenzene, chlorotrimethylsilane, and either Rieke-magnesium (Mg R ) or magnesium turnings in the presence of 1,2-dibromoethane as an entrainer (Mg e ). The most important advantages of these new protocols over the currently best-established procedure (1,2-dichlorobenzene, chlorotrimethylsilane, magnesium turnings, hexamethylphosphoramide) lie in the milder reaction conditions (Mg R : 08C, 2 h; Mg e : room temperature, 30 min vs. 100 8C, 2 days) and in the fact that the cancerogenic solvent hexa-A C H T U N G T R E N N U N G methylphosphoramide is avoided. Moreover, the improved protocols are also applicable for the highyield synthesis of 1,2,4,5-tetrakis(trimethylsilyl)benzene, 4-fluoro-1,2-bis(trimethylsilyl)benzene, 4-chloro-1,2-bis(trimethylsilyl)benzene, and 4,5-dichloro-1,2-bis(trimethylsilyl)benzene.

show abstract

9,10‐Dihydro‐9,10‐diboraanthracene: Supramolecular Structure and Use as a Building Block for Luminescent Conjugated Polymers

Cited by 77 publications

References 38 publications

Synthesis, Coupling, and Condensation Reactions of 1,2‐Diborylated Benzenes: An Experimental and Quantum‐Chemical Study

Synthesis, Coupling, and Condensation Reactions of 1,2‐Diborylated Benzenes: An Experimental and Quantum‐Chemical Study

Anorganische Chemie 2009

Improved Synthesis of 1,2‐Bis(trimethylsilyl)benzenes using Rieke‐Magnesium or the Entrainment Method

Contact Info

Product

Resources

About