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Formation of a radical tricationic tetraborane(4) by hydride abstraction from sp3-sp3-hybridized diboranes

The formation, electronic structure, and reactivity of the recently-reported radical tricationic tetraborane [B4(hpp)4]·3+ (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate), which features a planar rhomboid B4 unit and bridging bicyclic guanidinate (hpp) substituents, is reported. New exp...

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Hauptverfasser: Litters, Sebastian (VerfasserIn) , Kaifer, Elisabeth (VerfasserIn) , Himmel, Hans-Jörg (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 06 August 2016
In: European journal of inorganic chemistry
Year: 2016, Heft: 25, Pages: 4090-4098
ISSN:1099-0682
DOI:10.1002/ejic.201600629
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejic.201600629
Verlag, lizenzpflichtig, Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201600629
Volltext
Verfasserangaben:Sebastian Litters, Elisabeth Kaifer, and Hans-Jörg Himmel
Beschreibung
Zusammenfassung:The formation, electronic structure, and reactivity of the recently-reported radical tricationic tetraborane [B4(hpp)4]·3+ (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate), which features a planar rhomboid B4 unit and bridging bicyclic guanidinate (hpp) substituents, is reported. New experiments show that the tetraborane could be synthesized by hydride abstraction either in a very fast reaction from the electron-rich sp3?sp3-hybridized diborane [HB(hpp)]2, or in a very slow reaction from the cationic, less electron-rich sp3?sp3-hybridized diborane [HB(hpp)2BPCy3]+. The results argue for an electron-transfer in the rate-determining step of a complex reaction sequence. Quantum chemical calculations highlight the role of the hpp substituents for the stabilization of the radical tricationic tetraborane [B4(hpp)4]·3+. Further analysis shows that [B4(hpp)4]·3+ is highly reactive, and especially a very strong electrophile. This reactivity makes the compound very interesting because boron atoms in such a low oxidation state (<2) are expected to be strong nucleophiles.
Beschreibung:Im Titel ist die Zahl "3" jeweils hochgestellt
Gesehen am 27.05.2020
Beschreibung:Online Resource
ISSN:1099-0682
DOI:10.1002/ejic.201600629

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