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Fabrication of Uniform Nanoscale Cavities via Silicon Direct Wafer Bonding
Published on: January 9, 2014
Metal-Free Scission of the NO+ Triple Bond
Julie Willrett1, Harald Scherer1, Burkhard Butschke1
1Institut Für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Freiburg, Germany.
Abstract:
We report the facile and direct room temperature unimolecular scission of the N≡O+ triple bond, one of the strongest known chemical bonds with a bond dissociation energy of 1049 kJ mol-1. The reaction of NO[Al(ORF)4] (RF = C(CF3)3) and PNPt Bu (2,6-bis(di-tert-butylphosphinomethyl)pyridine) in CH2Cl2 yields the 1,2,3-diazaphospholo[1,5-a]pyridinium derivative [DAPPt Bu]+[Al(ORF)4]- (1), featuring the complete cleavage of the N≡O+ bond. At -30°C, the reaction intermediate [PNOPt Bu]+[Al(ORF)4]- (2), which contains the novel bridging P═N-O-P+ motif, can be isolated. Mechanistic insights were gained through quantum chemical calculations, which elucidated the formation pathways of 1 and 2, while NMR spectroscopic kinetic studies quantified the conversion rate from 2 to 1.
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