Azomethine derivatives. Part XI. Monomeric and dimeric arylmethyleneamino- and diarylmethyleneamino-boron compounds

Summerford, C.; Wade, Kenneth

doi:10.1039/j19700002010

Cited by 22 publications

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The other three resonances appear to be side products that form from the coordinated benzonitrile. The resonance at δ 177 was identified as benzophenone imine (by comparison with an authentic sample), while the resonance at δ 155 was confirmed by independent synthesis to be the allene analogue Ph 2 CNBPh 2 . The minor resonance at δ 165 was not identified.…”

Section: Resultsmentioning

confidence: 91%

See 1 more Smart Citation

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻

et al. 2011

View full text Add to dashboard Cite

The complex [Rh(dippe)(μ-Cl)]2 (1) was reduced with potassium metal to produce the highly reactive Rh–I species [Rh(dippe)(μ-K·THF)]2 (2). 2 was characterized by NMR spectroscopy (31P, 1H) and IR spectroscopy after forming the derivative K[Rh(dippe)(CO)2] (2a). The C–CN bond of benzonitrile was cleaved by oxidative addition when it was reacted stoichiometrically with 2 to form the anionic Rh(I) complex K[Rh(dippe)(CN)(Ph)] (3). 3 has been characterized by NMR spectroscopy (31P, 1H, 13C), and by the use of 13C-labeled benzonitrile. C–CN bond cleavage was also attempted by reacting benzonitrile with the zwitterionic complex [Rh(dippe)(η6-Ph-BPh3)] (4). A product 5 was formed from reaction with 2 equiv of benzonitrile. Reaction with 13C-labeled benzonitrile has ruled out the possibility of C–CN cleavage in this species, and a C–H bond activation pathway is operative instead.

show abstract

Section: Resultsmentioning

confidence: 91%

“…Carbon monoxide was purchased from Air Products Co. 1,2-Bis(diisopropylphosphino)ethane was synthesized according to a literature method . [Rh(dippe)(μ-Cl)] 2 ( 1 ) and Ph 2 CNBPh 2 were synthesized as previously reported. Sodium tetraphenylborate was purchased from Sigma-Aldrich, dried under vacuum, and stored under nitrogen.…”

Section: Methodsmentioning

confidence: 99%

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻

et al. 2011

View full text Add to dashboard Cite

show abstract

Beiträge zur Chemie des Bors, 183 Synthese und Struktur von Methylenboranen: Amino(9‐fluorenyliden)borane

Glaser¹,

Hanecker²,

Nöth³

et al. 1987

Chem. Ber.

View full text Add to dashboard Cite

Durch Dehydrohalogenierung von Amino(9-fluoreny1)halogenboranen sind metastabile Amino(9-fluoreny1iden)borane dann darstellbar, wenn die Amino-Gruppe einen erheblichen Raumanspruch aufweist, wie z. B. die Tetramethylpiperidino-(2), Ditert-butylamino-(5a) oder die tert-Butyl(trimethylsilyl)aminoGruppe (5b). [Bis(trimethylsilyl)amino](9-fluorenyliden)boran dimerisiert spontan zum 1,3-Diboracyclobutan-Derivat 7. IR-, NMR-und MS-Daten der Verbindungen werden diskutiert. Die Rontgenstrukturanalyse weist fur 2 ein Allen-analoges Bindungssystem nach. Die BC-Bindung besitzt rnit 1.422 (3) 8, Doppelbindungscharakter, denn sie ist um 0.22 8, kiirzer als die BC-Bindungen im Cyclodimeren 7, dessen Vierring-System nach Rontgenstrukturanalyse gefaltet ist.Die Allen-isosteren Bis(amino)bor(l +)-Kationen (Borinium-Ionen 2)) zeichnen sich durch eine erstaunlich grol3e Bildungstendenz aus. Mit dieser Verbindungsklasse isoelektronisch und mutmaI3lich auch isostrukturell sind Aminomethylenborane. Fur ihre Existenz ergaben sich Hinweise bei der Dehalosilylierung von Aminohalogen(silylorgany1)-boranen 3), der Dehydrohalogenierung von Aminohalogenorganylboranen') sowie bei der Pyrolyse von B-(Dimethylamino)borabarellenen4). Danach ist fur Aminomethylenborane nicht nur zu erwarten, daI3 sie Bor-Atome rnit der ungewohnlichen Koordinationszahl2 enthalten, sondern auch ein BC-und BN-System rnit Doppelbindungscharakter. Ein erstes Methylenboran beschreiben Klusik und Berndt fur ein fluktuierendes Cyclopropenylboran 5! Nach den Goubeauschen Regeln fur Systeme rnit stabilen Doppelbindungen@ zahlen Methylenborane zu den instabilen, d. h. zum ubergang in Einfachbindungen tendierenden Systemen, da die Summe der Elektronegativitat der an der Doppelbindung beteiligten Eleniente (B und C = 4.5) kleiner als 5 und die Differenz rnit 0.5 zwar nicht groI3, aber dennoch deutlich >O ist. Dies bestatigen die von Maier et aL4) erzeugten Methylenborane vom Typ XB = CHI, die selbst fur X = NMe2 nur bis 77 K in einer Matrix stabil sind. Folglich bedarf es sterischer Effekte fur eine hinreichende kinetische Stabilisierung von Methylenboranen, um sie strukturell zu charakterisieren. S yn thesenBisher durchgefuhrte Dehalogenierungen von Halogenorganyl(tetramethy1piperidino)boranen zeigen, daI3 bei 9-Fluorenyl-Derivaten die hochste Chance zur Erzeugung von Dehydrohalogenation of amino(9-fluorenyl)halogenoboranes allows the synthesis of metastable amino(9-tluorenylidene)boranes provided that the amino groups are sufficiently bulky1 as exemplified by the tetramethylpiperidino-(2), di-tert-butylamino-(5a), and tert-butyl(trimethylsilyl)amino groups (5 b), respectively. [Bis(trimethylsilyl)amino](9-fluorenylidene)borane dimerizes spontaneously to a 1,3-diboracyclobutane derivative 7. IR, NMR and MS data are discussed. The X-ray structure analysis of 2 reveals an allene type structure, its BC bond lengths 1.422 (3) 8, revealing double bond characteristics. This is ascertained by BC bonds in 7 which are 0.22 8, longer than in 2. The four-membered ring of 7 is folded.Me...

show abstract

ChemInform Abstract: AZOMETHIN‐DERIVATE 11. MITT. MONOMERE UND DIMERE ARYLMETHYLENAMINO‐ UND DIARYLMETHYLENAMINO‐BORVERBINDUNGEN

Summerford¹,

Wade²

1970

Chemischer Informationsdienst. Organische Chemie

View full text Add to dashboard Cite

show abstract

Azomethine derivatives. Part XI. Monomeric and dimeric arylmethyleneamino- and diarylmethyleneamino-boron compounds

Cited by 22 publications

References 0 publications

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻

Beiträge zur Chemie des Bors, 183 Synthese und Struktur von Methylenboranen: Amino(9‐fluorenyliden)borane

ChemInform Abstract: AZOMETHIN‐DERIVATE 11. MITT. MONOMERE UND DIMERE ARYLMETHYLENAMINO‐ UND DIARYLMETHYLENAMINO‐BORVERBINDUNGEN

Contact Info

Product

Resources

About

Azomethine derivatives. Part XI. Monomeric and dimeric arylmethyleneamino- and diarylmethyleneamino-boron compounds

Cited by 22 publications

References 0 publications

C–CN Bond Activation of Benzonitrile with [Rh–I(dippe)]−

C–CN Bond Activation of Benzonitrile with [Rh–I(dippe)]−

Beiträge zur Chemie des Bors, 183 Synthese und Struktur von Methylenboranen: Amino(9‐fluorenyliden)borane

ChemInform Abstract: AZOMETHIN‐DERIVATE 11. MITT. MONOMERE UND DIMERE ARYLMETHYLENAMINO‐ UND DIARYLMETHYLENAMINO‐BORVERBINDUNGEN

Contact Info

Product

Resources

About

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻

C–CN Bond Activation of Benzonitrile with [Rh^–I(dippe)]⁻