Open AccessA Preorganized Ditopic Borane as Highly Efficient One- or Two-Electron Trap
Author(s) -
Alexander Hübner,
Thomas Kaese,
Martin Diefenbach,
Burkhard Endeward,
Michael Bolte,
HansWolfram Lerner,
Max C. Holthausen,
Matthias Wagner
Publication year - 2015
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.5b01192
Subject(s) - chemistry , unpaired electron , delocalized electron , protonation , crystallography , electron paramagnetic resonance , comproportionation , borane , singlet state , nuclear magnetic resonance spectroscopy , spectroscopy , boron , stereochemistry , molecule , atomic physics , nuclear magnetic resonance , ion , organic chemistry , excited state , physics , electrode , quantum mechanics , electrochemistry , catalysis
Reduction of the bis(9-borafluorenyl)methane 1 with excess lithium furnishes the red dianion salt Li2[1]. The corresponding dark green monoanion radical Li[1] is accessible through the comproportionation reaction between 1 and Li2[1]. EPR spectroscopy on Li[1] reveals hyperfine coupling of the unpaired electron to two magnetically equivalent boron nuclei (a((11)B) = 5.1 ± 0.1 G, a((10)B) = 1.7 ± 0.2 G). Further coupling is observed to the unique B-CH-B bridgehead proton (a((1)H) = 7.2 ± 0.2 G) and to eight aromatic protons (a((1)H) = 1.4 ± 0.1 G). According to X-ray crystallography, the B···B distances continuously decrease along the sequence 1 → [1](•-) → [1](2-) with values of 2.534(2), 2.166(4), and 1.906(3) Å, respectively. Protonation of Li2[1] leads to the cyclic borohydride species Li[1H] featuring a B-H-B two-electron-three-center bond. This result strongly indicates a nucleophilic character of the boron atoms; the reaction can also be viewed as rare example of the protonation of an element-element σ bond. According to NMR spectroscopy, EPR spectroscopy, and quantum-chemical calculations, [1](2-) represents a closed-shell singlet without any spin contamination. Detailed wave function analyses of [1](•-) and [1](2-) reveal strongly localized interactions of the two boron pz-type orbitals, with small delocalized contributions of the 9-borafluorenyl π systems. Overall, our results provide evidence for a direct B-B one-electron and two-electron bonding interaction in [1](•-) and [1](2-), respectively.