1、Supplementary Information A Polycyclic Borazine Radical Cation: 1,2-B21,2-(MeN)2C6H42+Xiaochen Xie,aChristopher J. Adams,aMuhsen A. M. Al-Ibadi,b, cJohn E. McGrady,bNicholas C. Normana,* and Christopher A. Russella,* aUniversity of Bristol, School of Chemistry, Bristol, BS8 1TS, UK bDepartment of Ch
2、emistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK cPresent address: Department of Chemistry, University of Kufa, Najaf, Iraq. General Experimental B2(NMe2)41, 1,2-B21,2-(NH)2C6H422and AgAlOC(CF3)343were prepared according to literature procedures. A
3、ll other chemicals used were purchased from commercial sources and used as supplied. Elemental compositions (C, H and N) were determined by sealing samples in air-tight aluminium boats in a glove-box and recorded on a Carlo Erba EA1108 CHN elemental analyser. Solution NMR spectroscopy samples were p
4、repared using dry and degassed deuterated solvent in air-tight NMR tubes sealed with a Youngs tap; 11B NMR spectra were run on a Jeol Eclipse and/or Lambda 300 MHz spectrometers and referenced to external samples of BF3.OEt2. 1H and 13C NMR spectra were referenced to the internal solvent peaks. Elec
5、trochemical studies were performed on an EG 1H NMR (300 MHz, 25 C, CDCl3) = 7.08 (m, 4H, C6H4), 6.98 (m, 4H, C6H4), 3.37 (s, 12H, CH3); 13C-1H NMR (100 MHz, 25 C, CDCl3) = 139.8 (s, C6H4), 120.2 (s, C6H4), 115.1 (s, C6H4), 37.0 (s, CH3). Elemental Analysis: Calculated for C16H20B2N4: C, 66.27; H, 6.
6、95; N, 19.32; found C, 66.12; H, 7.06; N, 19.23%. X-ray crystallography: Crystals of 2 were mounted in inert oil and transferred to the cold gas stream of the diffractometer. Crystal data: C16H20B2N4, M = 289.98, Monoclinic, space group P21/c, a = 10.1884(4), b = 7.2885(3), c = 9.9017(4) , = 96.650(
7、2), U = 730.33(5) 3, Z = 2, Dc = 1.319 Mg/m3, = 0.71073 , (Mo-K) = 0.079 mm-1, F(000) = 308, T = 100(2)K, R1 = 0.0396 for 1404 reflections with I2(I). wR2 = 0.11156 for all 1689 reflections. CCDC 945386. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Soc
8、iety of Chemistry 2013Preparation of 2+: To a solid sample of AgAlOC(CF3)34 (0.070 g, 0.069 mmol), a solution of 2 (0.020 g, 0.069 mmol) in dichloromethane (10 cm3) was added at room temperature resulting in a green-black solution. This solution was stirred for 16 h in the absence of light and then
9、filtered through Celite, washed with dichloromethane (3 5 cm3) and then concentrated to ca. 5 cm3and cooled to 0 C overnight which afforded dark green crystals of 2+(0.021 g, 23%). Melting Point: decomposed 286-293 C to a black solid. Elemental Analysis: Calculated for C32H20AlB2F36N4O4: C, 30.57; H
10、, 1.60; N, 4.46; found: C, 30.42; H, 1.82; N, 4.36%. X-ray crystallography: Crystals of 2+AlOC(CF3)34were mounted in inert oil and transferred to the cold gas stream of the diffractometer. Crystal data: C32H20AlB2F36N4O4, M = 1257.12, Monoclinic, space group P21/c, a = 15.4396(11), b = 14.1144(9), c
11、 = 20.1020(12) , = 94.047(4), U = 4369.7(5) 3, Z = 4, Dc = 1.911 Mg/m3, = 0.71073 , (Mo-K) = 0.246 mm-1, F(000) = 2476, T = 100(2)K, R1 = 0.0516 for 11269 reflections with I2(I). wR2 = 0.1251 for all 15725 reflections. CCDC 945387. Electronic Supplementary Material (ESI) for Chemical CommunicationsT
12、his journal is The Royal Society of Chemistry 2013Computational methods Calculations were carried out using the B3LYP functional4implemented in Gaussian03.5Both structural optimization and the calculation of hyperfine coupling constants, a, was performed using the N07D basis set developed by Barone
13、and co-workers6which contains core-valence s functions optimised for the computation of a. The computed bond lengths are in excellent agreement with experiment, both for 2+and its one-electron reduced precursor, 2. Table of optimised bond lengths Table S1. Selected X-ray and computed bond lengths ()
14、 for 2 and 2+(labelled according to figure above). 2 2+X-ray Computed X-ray Computed B-B 1.650(2) 1.65 1.643(3) 1.65 B-N 1.426(2), 1.430(2) 1.44 1.427(7), 1.423(7) 1.44 C(1)-N(1) 1.470(1) 1.47 1.467(3) 1.48 C(3)-N(1), C(4)-N(2) 1.417(2), 1.417(2) 1.42 1.396(3), 1.392(3) 1.40 C(3)-C(4) 1.429(2) 1.43
15、1.435(3) 1.44 C(3)-C(8), C(4)-C(5) 1.400(2), 1.398(2) 1.41 1.386(3), 1.410(3) 1.40 C(5)-C(6), C(7)-C(8) 1.389(2), 1.387(2) 1.39 1.410(3), 1.370(3) 1.38 C(6)-C(7) 1.379(2) 1.39 1.386(3) 1.40 Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemis
16、try 2013Table S2. Comparison of computed isotropic hyperfine values for 2+(G) with the final values from the simulation. DFT Simulation B 2.48 2.12 N 3.34 3.87 C(3)/C(4) -0.67 C(5)/C(8) -0.75 C(6)/C(7) 0.77 C(1)/C(2) -1.80 H(5)/H(8) -0.16 -0.32 H(6)/H(7) 1.40 -1.49 H(Me) 3.57 3.58 References 1. M. J
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