Supplementary information
doi: 10.1038/nchem.513 Supplementary Information for
“Dianionic Species with a Bond Consisting of Two
Pentacoordinated Silicon Atoms”
Naokazu Kano
†,*, Hideaki Miyake
†, Keishi Sasaki
†, Takayuki
Kawashima
†,*, Naomi Mizorogi
‡, and Shigeru Nagase
‡Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan
Contents of the Supplementary Information
General experimental procedures S2
Experimental procedures for 2a-c and 3 S2-S4
NMR spectral charts of 2a-c and 3 S5-S13
Cyclic voltammogram of 2b, 3 and 4 S14-S15
X-ray Crystallographic Analysis of 2c S16-S26
Theoretical calculation of 2d, 3, 4, and 5 S27-S44
Complete list of the references 12, 17, 20, and 23 S44
Supplementary information
doi: 10.1038/nchem.513General experimental procedures. Solvents were purified before use by reported
methods. All reactions except the synthesis of disilicate 2a were carried out in the air. All melting points are uncorrected. All NMR spectra were measured with a JEOL AL400 spectrometer. Tetramethylsilane was used as an external standard
for the 1H-NMR (400 MHz), 13C-NMR (100 MHz), and 29Si-NMR (79 MHz)
spectra. Lithium chloride and CF3CO2H were used as an external standard for the
7Li-NMR (155 MHz) and the 19F-NMR (376 MHz) spectra, respectively.
FAB-Mass spectral data were obtained on a JEOL JMS-SX102 spectrometer. Elemental analyses were performed by the Microanalytical Laboratory of Department of Chemistry, Faculty of Science, The University of Tokyo. UV/vis spectra (Supplementary Figure 18) were obtained on UV/vis spectrophotometer V-530 (JASCO). Silane 1 was prepared according to a literature.1 Compound 2a with three molecules of 1,2-dimethoxyethane (DME) was formed before reprecipitation from wet acetone/hexane, as written in the Methods section, and it was used for the syntheses of 2b and 2c.
Synthesis of disilicate 2b.
An aqueous solution (2 mL) of tetrabutylammonium bromide (24 mg, 74 µmol) was added to a solution of disilicate 2a (20 µmol) in water (1 mL) and acetone (1 mL) at room temperature. After the solution was stirred for 10 minutes at room temperature, solvents were removed under reduced pressure to give crude solids. The solids were washed with water and dried to give disilicate 2b (31 mg, 100%) as white solids. Quantitative formation of 2b was confirmed by 1H- and 19F-NMR spectroscopy. Recrystallization from acetone-water gave colorless crystals suitable for elemental analysis. 2b: Colorless crystals (acetone-hexane); m.p.: 170
˚C (decomp.); 1H-NMR (400 MHz, acetone-d 6): ! 0.97 (t, J = 7.4 Hz, 24H), 1.36-1.47 (m, 16H), 1.75-1.85 (m, 16H), 3.38-3.44 (m, 16H), 6.87-6.95 (m, 4H), 7.05-7.13 (m, 8H), 8.38-8.44 (br s, 4H); 13C{1H}-NMR (100 MHz, acetone-d 6): ! 13.8 (s), 20.3 (s), 24.3 (s), 59.2-59.4 (m), 83.7 (sept, 2J CF = 28 Hz), 122.3 (s), 125.2 (q, 1 JCF = 290 Hz), 126.0 (q, 1JCF = 292 Hz), 126.1 (s), 126.9 (s), 140.0 (s), 141.4 (s), 149.4 (s); 19F-NMR (376 MHz, acetone-d 6): ! –75.9 to –75.6 (m, 12F), –74.8 to –74.6 (m, 12F); 29Si-NMR (79 MHz, acetone-d 6): ! –63.6 (s); MS (FAB,
Supplementary information
doi: 10.1038/nchem.513analysis (% calcd, % found for C6 8H8 8F24N2O4Si2): C (54.10, 53.99), H (5.88, 6.05), N (1.86, 1.60).
Synthesis of disilicate 2c.
An aqueous solution (2 mL) of benzyltrimethylammonium chloride (91 mg, 490 mmol) was added to a solution of disilicate 2a (50 µmol) in water (5 mL) and acetone (5 mL) at room temperature. After the solution was stirred overnight at room temperature, solvents were removed under reduced pressure to give crude solids. The solids were washed with water and dried to give disilicate 2c (35 mg, 52%) as white solids. Recrystallization from acetone-THF gave colorless crystals suitable for elemental analysis. 2c: Colorless crystals; m.p.: 269 ˚C (decomp.);
1H-NMR (400 MHz, acetone-d 6): ! 3.35 (s, 18H), 4.77 (s, 4H), 6.88-6.92 (m, 4H), 7.05-7.10 (m, 8H), 7.53-7.62 (m, 6H), 7.66-7.70 (m, 4H), 8.40-8.44 (m, 4H); 13C{1H}-NMR (100 MHz, acetone-d 6): ! 53.1-53.3 (m), 70.1-70.2 (m), 83.2-84.2 (m), 122.3 (s), 125.2 (q, 1J CF = 290 Hz), 126.0 (q, 1JCF = 292 Hz), 126.0 (s), 126.7 (s), 126.8 (s), 129.9 (s), 131.5 (s), 133.6 (s), 139.8 (s), 141.3 (s), 149.5 (s); 19F-NMR (376 MHz, acetone-d 6): ! –75.8 to –75.6 (m, 12F), –74.8 to –74.6 (m, 12F); 2 9Si-NMR (79 MHz, acetone-d 6): ! –63.3 (s); MS (FAB, negative) m/z: 1174 [M–BnMe3N]–; MS (FAB, positive) m/z: 150 [BnMe
3N]+; analysis (% calcd, % found for C56H48F24N2O4Si2): C (50.76, 50.72), H (3.65, 3.68), N (2.11, 2.03).
Synthesis of disilane 3 from disilicate 2a.
Hydrochloric acid (1 mol·L-1, 2 mL) was added to diethyl ether (Et 2O) suspension (20 mL) of disilicate 2a·(H2O)2 (106 mg, 0.10 mmol) at room temperature and the mixture was stirred for 1 hour. After the organic phase was separated, aqueous phase was extracted with diethyl ether and the combined organic phase was dried with anhydrous magnesium sulfate. Evaporation of the solvent gave almost pure disilane 3 (90.0 mg, 88%). Pure colorless crystals of
Supplementary information
doi: 10.1038/nchem.513disilane 3 was obtained by recrystallization from acetone. 3: Colorless crystals (acetone); m.p.: 180 ˚C (decomp.); 1H-NMR (400 MHz, acetone-d
6): ! 3.77 (br, 2H), 7.38-7.53 (br s, 12H), 8.35 (br s, 4H); 1 3C{1H}-NMR (100 MHz, acetone-d 6): ! 82.8 (sept, 2J CF = 30 Hz), 123.1 (q, 1JCF = 287 Hz), 123.6 (q, 1JCF = 287 Hz), 124.8 (s), 130.1 (s), 130.6 (s), 136.1 (m), 137.3 (s), 137.7 (m); 19F-NMR (376 MHz, acetone-d6): ! –76.4 to –75.6 (m, 12F), –75.5 to –75.3 (br s, 12F); 29Si-NMR (79 MHz, acetone-d 6): ! –14.4 (s); UV/vis (CH2Cl2): ! 236 nm (" = 2.9"104); MS (FAB, negative) m/z: 1025 [M–H]–; analysis (% calcd, found for C36H18F24N2O4Si2): C (42.12, 41.85), H (1.77, 1.77).
Synthesis of disilane 3 from disilicate 2b.
Similarly to the procedure described above, treatment of disilicate 2b (151 mg, 0.10 mmol) with hydrochloric acid (1 mol·L-1, 2 mL) in Et
2O (20 mL) at room temperature followed by stirring for 1 hour gave disilane 3 (84.4 mg, 82%).
Conversion of disilane 3 to disilicate 2a.
Disilane 3 (51 mg, 50 µmol) in THF (10 mL) was added to lithium hydride (4 mg, 0.5 mmol) at room temperature and the solution was stirred for 1 hour. The reaction mixture was filtered through Celite, and the filtrate was evaporated under reduced pressure to give white solids. Reprecipitation of the solids from wet acetone/hexane gave disilane 2a·(H2O)2 (44 mg, 82%).
Supplementary information
doi: 10.1038/nchem.513NMR spectral charts of compounds 2a-c and 3.
The 1H-, 7Li-, 13C-, 19F-, and 29Si-NMR spectral charts of disilicates 2a-c and disilane 3 are shown in Supplementary Figures 1-17.
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doi: 10.1038/nchem.513Supplementary Figure 2. 7Li-NMR spectrum of 2a.
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doi: 10.1038/nchem.513Supplementary Figure 4. 19F-NMR spectrum of 2a.
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doi: 10.1038/nchem.513Supplementary Figure 6. 1H-NMR spectrum of 2b.
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doi: 10.1038/nchem.513Supplementary Figure 8. 19F-NMR spectrum of 2b.
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doi: 10.1038/nchem.513Supplementary Figure 10. 1H-NMR spectrum of 2c.
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doi: 10.1038/nchem.513Supplementary Figure 12. 19F-NMR spectrum of 2c.
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doi: 10.1038/nchem.513Supplementary Figure 14. 1H-NMR spectrum of 3.
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doi: 10.1038/nchem.513Supplementary Figure 16. 19F-NMR spectrum of 3.
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doi: 10.1038/nchem.513Cyclic voltammogram of disilicate 2b and disilanes 3 and 4.
The electrochemical experiments were carried out with an Electrochemical Analyzer Model 620A (ALS/CH Instruments) using a glassy carbon rod working electrode, a Pt wire counter electrode, and a Fc/Fc+ reference electrode (Fc: ferrocene). The solutions were degassed prior to the measurements. The measurements were carried out in 1 mmol·L- 1 dichloromethane solution of 2b, 3, or 4 containing 0.1 mol·L-1 n-Bu
4NClO4 as a supporting electrolyte with scan rates of 0.05 V·s-1 at room temperature. The cyclic voltammograms of 2b, 3, and 4 are shown in Supplementary Figures 18-20, respectively.
Supplementary Figure 18. Cyclic voltammogram of disilicate 2b.
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doi: 10.1038/nchem.513Supplementary Figure 19. Cyclic voltammogram of disilane 3.
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doi: 10.1038/nchem.513X-ray crystallographic analysis
Colorless crystals of 2c were obtained by recrystallization from acetone-THF and used for the X-ray diffraction data collection on a Rigaku Mercury charge-coupled device diffractometer with a graphite-monochromated Mo–K# radiation. Data were collected and processed using CrystalClear (Rigaku).2 The data were corrected for Lorentz and polarization effects. The structure was solved by direct methods (SHELXS-97) and expanded using Fourier techniques.3 The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined isotropically. Crystal data are summarized in Supplementary Table 1. Atomic coordinates and equivalent isotropic displacement parameters are summarized in Supplementary Table 2. Bond lengths and angles are shown in Supplementary Table 3. Hydrogen coordinates and isotropic displacement parameters are shown in Supplementary Table 4. Torsion angles are shown in Supplementary Table 5. More crystal data are available at the Cambridge Crystallographic Database Centre, deposition no. CCDC 692252.
Supplementary information
doi: 10.1038/nchem.513Supplementary Table 1. Crystal data and structure refinement for disilicate 2c.
Empirical formula C56 H48 F24 N2 O4 Si2
Formula weight 1325.14
Temperature 120(2) K
Wavelength 0.71070 Å
Crystal system Monoclinic
Space group C2/c
Unit cell dimensions a = 17.113(3) Å # = 90°
b = 16.1501(17) Å $ = 107.588(2)° c = 20.618(4) Å % = 90° Volume 5431.9(14) Å3 Z 4 Density (calculated) 1.620 Mg/m3 Absorption coefficient 0.199 mm-1 F(000) 2696 Crystal size 0.55 x 0.40 x 0.11 mm3
Theta range for data collection 3.00 to 25.00°.
Index ranges -20<=h<=15, -19<=k<=19, -17<=l<=24
Reflections collected 17086
Independent reflections 4701 [R(int) = 0.0374]
Completeness to theta = 25.00° 98.5%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.9804 and 0.8985
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 4701 / 0 / 401
Goodness-of-fit on F2 1.072
Final R indices [I>2sigma(I)] R1 = 0.0374, wR2 = 0.1015
R indices (all data) R1 = 0.0433, wR2 = 0.1075
Supplementary information
doi: 10.1038/nchem.513Supplementary Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for disilicate 2c. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x y z U(eq) Si(1) 0 3252(1) 2500 13(1) C(1) -527(1) 3799(1) 3073(1) 15(1) C(2) -1357(1) 3966(1) 2947(1) 19(1) C(3) -1655(1) 4314(1) 3440(1) 22(1) C(4) -1120(1) 4508(1) 4076(1) 23(1) C(5) -290(1) 4368(1) 4214(1) 23(1) C(6) 1(1) 4012(1) 3714(1) 16(1) C(7) 892(1) 3807(1) 3785(1) 16(1) C(8) 1377(1) 4622(1) 3807(1) 22(1) F(1) 1046(1) 5070(1) 3251(1) 29(1) F(2) 1393(1) 5111(1) 4341(1) 31(1) F(3) 2159(1) 4488(1) 3839(1) 33(1) C(9) 1285(1) 3294(1) 4430(1) 19(1) F(4) 834(1) 2630(1) 4452(1) 25(1) F(5) 1363(1) 3716(1) 5016(1) 24(1) F(6) 2036(1) 3033(1) 4470(1) 29(1) O(1) 942(1) 3343(1) 3240(1) 16(1) Si(2) 0 1788(1) 2500 13(1) C(10) 493(1) 1239(1) 3344(1) 15(1) C(11) 1321(1) 1063(1) 3649(1) 18(1) C(12) 1597(1) 739(1) 4301(1) 21(1) C(13) 1048(1) 578(1) 4662(1) 21(1) C(14) 224(1) 729(1) 4371(1) 19(1) C(15) -44(1) 1057(1) 3713(1) 15(1) C(16) -933(1) 1250(1) 3313(1) 16(1) C(17) -1388(1) 423(1) 3081(1) 20(1) F(7) -1054(1) 16(1) 2666(1) 26(1) F(8) -1363(1) -105(1) 3593(1) 25(1) F(9) -2181(1) 530(1) 2739(1) 30(1) C(18) -1371(1) 1738(1) 3743(1) 21(1) F(10) -935(1) 2394(1) 4035(1) 27(1)
Supplementary information
doi: 10.1038/nchem.513 F(12) -2101(1) 2024(1) 3362(1) 31(1) O(2) -964(1) 1708(1) 2746(1) 15(1) N(1) 1320(1) 2586(1) 6690(1) 23(1) C(19) 2171(1) 2551(2) 6634(1) 38(1) C(20) 1113(2) 3458(1) 6799(1) 51(1) C(21) 1287(1) 2069(1) 7276(1) 36(1) C(22) 741(1) 2248(1) 6025(1) 31(1) C(23) -142(1) 2191(1) 5998(1) 24(1) C(24) -681(1) 2850(1) 5762(1) 37(1) C(25) -1500(1) 2771(1) 5713(1) 39(1) C(26) -1797(1) 2038(1) 5890(1) 33(1) C(27) -1271(1) 1383(1) 6118(1) 32(1) C(28) -452(1) 1456(1) 6171(1) 28(1)Supplementary Table 3. Bond lengths [Å] and angles [°] for disilicate 2c.
Si(1)-O(1) 1.8611(11) Si(1)-O(1)#1 1.8611(11) Si(1)-C(1) 1.9058(16) Si(1)-C(1)#1 1.9058(16) Si(1)-Si(2) 2.3647(9) C(1)-C(2) 1.390(2) C(1)-C(6) 1.400(2) C(2)-C(3) 1.387(2) C(2)-H(1) 0.9500 C(3)-C(4) 1.390(3) C(3)-H(2) 0.9500 C(4)-C(5) 1.380(3) C(4)-H(3) 0.9500 C(5)-C(6) 1.397(2) C(5)-H(4) 0.9500 C(6)-C(7) 1.524(2) C(7)-O(1) 1.3747(19) C(7)-C(9) 1.539(2) C(7)-C(8) 1.548(2) C(8)-F(1) 1.330(2) C(8)-F(3) 1.338(2) C(8)-F(2) 1.349(2) C(9)-F(4) 1.330(2) C(9)-F(6) 1.331(2) C(9)-F(5) 1.3585(19) Si(2)-O(2) 1.8714(11) Si(2)-O(2)#1 1.8714(11) Si(2)-C(10)#1 1.9073(16) Si(2)-C(10) 1.9073(16) C(10)-C(15) 1.390(2) C(10)-C(11) 1.395(2) C(11)-C(12) 1.384(2)
Supplementary information
doi: 10.1038/nchem.513 C(11)-H(5) 0.9500 C(12)-C(13) 1.389(3) C(12)-H(6) 0.9500 C(13)-C(14) 1.378(3) C(13)-H(7) 0.9500 C(14)-C(15) 1.398(2) C(14)-H(8) 0.9500 C(15)-C(16) 1.529(2) C(16)-O(2) 1.3719(19) C(16)-C(18) 1.539(2) C(16)-C(17) 1.546(2) C(17)-F(7) 1.336(2) C(17)-F(9) 1.338(2) C(17)-F(8) 1.3475(19) C(18)-F(10) 1.331(2) C(18)-F(12) 1.342(2) C(18)-F(11) 1.3453(19) N(1)-C(21) 1.484(2) N(1)-C(20) 1.486(3) N(1)-C(19) 1.496(3) N(1)-C(22) 1.530(2) C(19)-H(9) 0.9800 C(19)-H(10) 0.9800 C(19)-H(11) 0.9800 C(20)-H(12) 0.9800 C(20)-H(13) 0.9800 C(20)-H(14) 0.9800 C(21)-H(15) 0.9800 C(21)-H(16) 0.9800 C(21)-H(17) 0.9800 C(22)-C(23) 1.499(3) C(22)-H(18) 0.9900 C(22)-H(19) 0.9900 C(23)-C(28) 1.390(3) C(23)-C(24) 1.395(3) C(24)-C(25) 1.380(3) C(24)-H(20) 0.9500 C(25)-C(26) 1.382(3) C(25)-H(21) 0.9500 C(26)-C(27) 1.376(3) C(26)-H(22) 0.9500 C(27)-C(28) 1.378(3) C(27)-H(23) 0.9500 C(28)-H(24) 0.9500 O(1)-Si(1)-O(1)#1 170.95(8) O(1)-Si(1)-C(1) 84.87(6) O(1)#1-Si(1)-C(1) 90.93(6) O(1)-Si(1)-C(1)#1 90.93(6) O(1)#1-Si(1)-C(1)#1 84.87(6) C(1)-Si(1)-C(1)#1 124.74(10) O(1)-Si(1)-Si(2) 94.52(4) O(1)#1-Si(1)-Si(2) 94.52(4) C(1)-Si(1)-Si(2) 117.63(5) C(1)#1-Si(1)-Si(2) 117.63(5) C(2)-C(1)-C(6) 117.35(15) C(2)-C(1)-Si(1) 128.50(12) C(6)-C(1)-Si(1) 114.05(12) C(3)-C(2)-C(1) 121.62(16) C(3)-C(2)-H(1) 119.2Supplementary information
doi: 10.1038/nchem.513 C(1)-C(2)-H(1) 119.2 C(2)-C(3)-C(4) 119.91(16) C(2)-C(3)-H(2) 120.0 C(4)-C(3)-H(2) 120.0 C(5)-C(4)-C(3) 120.06(16) C(5)-C(4)-H(3) 120.0 C(3)-C(4)-H(3) 120.0 C(4)-C(5)-C(6) 119.32(16) C(4)-C(5)-H(4) 120.3 C(6)-C(5)-H(4) 120.3 C(5)-C(6)-C(1) 121.71(16) C(5)-C(6)-C(7) 125.99(15) C(1)-C(6)-C(7) 112.29(14) O(1)-C(7)-C(6) 110.35(13) O(1)-C(7)-C(9) 107.11(13) C(6)-C(7)-C(9) 111.30(13) O(1)-C(7)-C(8) 108.77(13) C(6)-C(7)-C(8) 109.27(14) C(9)-C(7)-C(8) 109.99(13) F(1)-C(8)-F(3) 106.83(14) F(1)-C(8)-F(2) 106.46(14) F(3)-C(8)-F(2) 106.26(14) F(1)-C(8)-C(7) 110.72(13) F(3)-C(8)-C(7) 112.54(15) F(2)-C(8)-C(7) 113.58(14) F(4)-C(9)-F(6) 107.55(14) F(4)-C(9)-F(5) 106.04(13) F(6)-C(9)-F(5) 105.73(13) F(4)-C(9)-C(7) 110.88(13) F(6)-C(9)-C(7) 112.67(14) F(5)-C(9)-C(7) 113.53(13) C(7)-O(1)-Si(1) 117.40(10) O(2)-Si(2)-O(2)#1 172.13(8) O(2)-Si(2)-C(10)#1 91.85(6) O(2)#1-Si(2)-C(10)#1 84.48(6) O(2)-Si(2)-C(10) 84.48(6) O(2)#1-Si(2)-C(10) 91.85(6) C(10)#1-Si(2)-C(10) 124.60(10) O(2)-Si(2)-Si(1) 93.94(4) O(2)#1-Si(2)-Si(1) 93.94(4) C(10)#1-Si(2)-Si(1) 117.70(5) C(10)-Si(2)-Si(1) 117.70(5) C(15)-C(10)-C(11) 117.29(15) C(15)-C(10)-Si(2) 114.51(12) C(11)-C(10)-Si(2) 127.99(12) C(12)-C(11)-C(10) 121.16(16) C(12)-C(11)-H(5) 119.4 C(10)-C(11)-H(5) 119.4 C(11)-C(12)-C(13) 120.23(16) C(11)-C(12)-H(6) 119.9 C(13)-C(12)-H(6) 119.9 C(14)-C(13)-C(12) 120.15(16) C(14)-C(13)-H(7) 119.9 C(12)-C(13)-H(7) 119.9 C(13)-C(14)-C(15) 118.79(16) C(13)-C(14)-H(8) 120.6 C(15)-C(14)-H(8) 120.6 C(10)-C(15)-C(14) 122.35(16) C(10)-C(15)-C(16) 112.12(14) C(14)-C(15)-C(16) 125.52(15)Supplementary information
doi: 10.1038/nchem.513 O(2)-C(16)-C(15) 110.19(13) O(2)-C(16)-C(18) 108.32(13) C(15)-C(16)-C(18) 111.84(13) O(2)-C(16)-C(17) 108.44(13) C(15)-C(16)-C(17) 108.47(13) C(18)-C(16)-C(17) 109.51(13) F(7)-C(17)-F(9) 106.66(14) F(7)-C(17)-F(8) 105.84(13) F(9)-C(17)-F(8) 106.40(13) F(7)-C(17)-C(16) 110.50(13) F(9)-C(17)-C(16) 112.70(14) F(8)-C(17)-C(16) 114.22(13) F(10)-C(18)-F(12) 106.58(14) F(10)-C(18)-F(11) 107.10(14) F(12)-C(18)-F(11) 106.01(14) F(10)-C(18)-C(16) 111.42(14) F(12)-C(18)-C(16) 111.58(14) F(11)-C(18)-C(16) 113.72(14) C(16)-O(2)-Si(2) 117.28(9) C(21)-N(1)-C(20) 109.93(18) C(21)-N(1)-C(19) 108.58(16) C(20)-N(1)-C(19) 109.23(17) C(21)-N(1)-C(22) 110.83(15) C(20)-N(1)-C(22) 110.80(16) C(19)-N(1)-C(22) 107.39(15) N(1)-C(19)-H(9) 109.5 N(1)-C(19)-H(10) 109.5 H(9)-C(19)-H(10) 109.5 N(1)-C(19)-H(11) 109.5 H(9)-C(19)-H(11) 109.5 H(10)-C(19)-H(11) 109.5 N(1)-C(20)-H(12) 109.5 N(1)-C(20)-H(13) 109.5 H(12)-C(20)-H(13) 109.5 N(1)-C(20)-H(14) 109.5 H(12)-C(20)-H(14) 109.5 H(13)-C(20)-H(14) 109.5 N(1)-C(21)-H(15) 109.5 N(1)-C(21)-H(16) 109.5 H(15)-C(21)-H(16) 109.5 N(1)-C(21)-H(17) 109.5 H(15)-C(21)-H(17) 109.5 H(16)-C(21)-H(17) 109.5 C(23)-C(22)-N(1) 115.33(15) C(23)-C(22)-H(18) 108.4 N(1)-C(22)-H(18) 108.4 C(23)-C(22)-H(19) 108.4 N(1)-C(22)-H(19) 108.4 H(18)-C(22)-H(19) 107.5 C(28)-C(23)-C(24) 118.57(18) C(28)-C(23)-C(22) 120.03(18) C(24)-C(23)-C(22) 121.29(19) C(25)-C(24)-C(23) 120.3(2) C(25)-C(24)-H(20) 119.8 C(23)-C(24)-H(20) 119.8 C(24)-C(25)-C(26) 120.4(2) C(24)-C(25)-H(21) 119.8 C(26)-C(25)-H(21) 119.8 C(27)-C(26)-C(25) 119.6(2) C(27)-C(26)-H(22) 120.2Supplementary information
doi: 10.1038/nchem.513 C(25)-C(26)-H(22) 120.2 C(26)-C(27)-C(28) 120.41(19) C(26)-C(27)-H(23) 119.8 C(28)-C(27)-H(23) 119.8 C(27)-C(28)-C(23) 120.68(18) C(27)-C(28)-H(24) 119.7 C(23)-C(28)-H(24) 119.7Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/2
Supplementary Table 4. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2 x 103) for disilicate 2c.
x y z U(eq) H(1) -1728 3839 2513 23 H(2) -2225 4419 3343 27 H(3) -1325 4737 4417 28 H(4) 80 4512 4644 27 H(5) 1702 1166 3406 21 H(6) 2164 627 4501 25 H(7) 1242 364 5112 25 H(8) -156 611 4612 23 H(9) 2556 2785 7046 57 H(10) 2196 2871 6237 57 H(11) 2318 1973 6582 57 H(12) 541 3491 6797 76 H(13) 1192 3806 6434 76 H(14) 1472 3653 7239 76 H(15) 1692 2270 7691 54 H(16) 1409 1492 7195 54 H(17) 738 2103 7329 54 H(18) 782 2606 5647 38 H(19) 931 1688 5947 38
Supplementary information
doi: 10.1038/nchem.513 H(20) -483 3355 5634 44 H(21) -1861 3225 5557 47 H(22) -2362 1985 5855 40 H(23) -1474 877 6240 38 H(24) -95 999 6326 34Supplementary Table 5. Torsion angles [°] for disilicate 2c.
O(1)-Si(1)-C(1)-C(2) -174.57(15) O(1)#1-Si(1)-C(1)-C(2) 13.45(15) C(1)#1-Si(1)-C(1)-C(2) 97.85(15) Si(2)-Si(1)-C(1)-C(2) -82.15(15) O(1)-Si(1)-C(1)-C(6) 1.57(12) O(1)#1-Si(1)-C(1)-C(6) -170.41(12) C(1)#1-Si(1)-C(1)-C(6) -86.00(12) Si(2)-Si(1)-C(1)-C(6) 94.00(12) C(6)-C(1)-C(2)-C(3) -1.3(2) Si(1)-C(1)-C(2)-C(3) 174.74(13) C(1)-C(2)-C(3)-C(4) 0.3(3) C(2)-C(3)-C(4)-C(5) 1.1(3) C(3)-C(4)-C(5)-C(6) -1.6(3) C(4)-C(5)-C(6)-C(1) 0.6(3) C(4)-C(5)-C(6)-C(7) -179.20(16) C(2)-C(1)-C(6)-C(5) 0.8(2) Si(1)-C(1)-C(6)-C(5) -175.76(13) C(2)-C(1)-C(6)-C(7) -179.37(14) Si(1)-C(1)-C(6)-C(7) 4.03(17) C(5)-C(6)-C(7)-O(1) 170.17(15) C(1)-C(6)-C(7)-O(1) -9.61(19) C(5)-C(6)-C(7)-C(9) 51.4(2) C(1)-C(6)-C(7)-C(9) -128.40(15) C(5)-C(6)-C(7)-C(8) -70.3(2) C(1)-C(6)-C(7)-C(8) 109.94(15) O(1)-C(7)-C(8)-F(1) 62.73(18) C(6)-C(7)-C(8)-F(1) -57.80(18) C(9)-C(7)-C(8)-F(1) 179.75(13) O(1)-C(7)-C(8)-F(3) -56.76(17) C(6)-C(7)-C(8)-F(3) -177.29(13) C(9)-C(7)-C(8)-F(3) 60.26(18) O(1)-C(7)-C(8)-F(2) -177.56(13) C(6)-C(7)-C(8)-F(2) 61.92(18) C(9)-C(7)-C(8)-F(2) -60.54(19) O(1)-C(7)-C(9)-F(4) -67.83(17) C(6)-C(7)-C(9)-F(4) 52.87(18) C(8)-C(7)-C(9)-F(4) 174.12(13) O(1)-C(7)-C(9)-F(6) 52.77(18) C(6)-C(7)-C(9)-F(6) 173.48(13) C(8)-C(7)-C(9)-F(6) -65.28(18) O(1)-C(7)-C(9)-F(5) 172.92(12) C(6)-C(7)-C(9)-F(5) -66.38(18)
Supplementary information
doi: 10.1038/nchem.513 C(8)-C(7)-C(9)-F(5) 54.87(19) C(6)-C(7)-O(1)-Si(1) 11.37(16) C(9)-C(7)-O(1)-Si(1) 132.67(11) C(8)-C(7)-O(1)-Si(1) -108.49(13) C(1)-Si(1)-O(1)-C(7) -7.73(11) C(1)#1-Si(1)-O(1)-C(7) 117.07(11) Si(2)-Si(1)-O(1)-C(7) -125.11(10) O(1)-Si(1)-Si(2)-O(2) 113.36(5) O(1)#1-Si(1)-Si(2)-O(2) -66.64(5) C(1)-Si(1)-Si(2)-O(2) 26.79(6) C(1)#1-Si(1)-Si(2)-O(2) -153.21(6) O(1)-Si(1)-Si(2)-O(2)#1 -66.64(5) O(1)#1-Si(1)-Si(2)-O(2)#1 113.36(5) C(1)-Si(1)-Si(2)-O(2)#1 -153.21(6) C(1)#1-Si(1)-Si(2)-O(2)#1 26.79(6) O(1)-Si(1)-Si(2)-C(10)#1 -152.47(6) O(1)#1-Si(1)-Si(2)-C(10)#1 27.53(6) C(1)-Si(1)-Si(2)-C(10)#1 120.96(8) C(1)#1-Si(1)-Si(2)-C(10)#1 -59.04(8) O(1)-Si(1)-Si(2)-C(10) 27.53(6) O(1)#1-Si(1)-Si(2)-C(10) -152.47(6) C(1)-Si(1)-Si(2)-C(10) -59.04(8) C(1)#1-Si(1)-Si(2)-C(10) 120.96(8) O(2)-Si(2)-C(10)-C(15) -0.25(12) O(2)#1-Si(2)-C(10)-C(15) -173.27(12) C(10)#1-Si(2)-C(10)-C(15) -88.69(12) Si(1)-Si(2)-C(10)-C(15) 91.31(12) O(2)-Si(2)-C(10)-C(11) -174.80(15) O(2)#1-Si(2)-C(10)-C(11) 12.18(15) C(10)#1-Si(2)-C(10)-C(11) 96.76(15) Si(1)-Si(2)-C(10)-C(11) -83.24(15) C(15)-C(10)-C(11)-C(12) -1.6(2) Si(2)-C(10)-C(11)-C(12) 172.83(13) C(10)-C(11)-C(12)-C(13) 0.4(3) C(11)-C(12)-C(13)-C(14) 0.9(3) C(12)-C(13)-C(14)-C(15) -1.1(3) C(11)-C(10)-C(15)-C(14) 1.4(2) Si(2)-C(10)-C(15)-C(14) -173.73(13) C(11)-C(10)-C(15)-C(16) -177.94(14) Si(2)-C(10)-C(15)-C(16) 6.89(17) C(13)-C(14)-C(15)-C(10) -0.1(2) C(13)-C(14)-C(15)-C(16) 179.17(15) C(10)-C(15)-C(16)-O(2) -12.24(19) C(14)-C(15)-C(16)-O(2) 168.40(15) C(10)-C(15)-C(16)-C(18) -132.79(15) C(14)-C(15)-C(16)-C(18) 47.9(2) C(10)-C(15)-C(16)-C(17) 106.33(15) C(14)-C(15)-C(16)-C(17) -73.0(2) O(2)-C(16)-C(17)-F(7) 57.45(17) C(15)-C(16)-C(17)-F(7) -62.22(17) C(18)-C(16)-C(17)-F(7) 175.47(13) O(2)-C(16)-C(17)-F(9) -61.78(17) C(15)-C(16)-C(17)-F(9) 178.56(13) C(18)-C(16)-C(17)-F(9) 56.24(17) O(2)-C(16)-C(17)-F(8) 176.64(13) C(15)-C(16)-C(17)-F(8) 56.97(18) C(18)-C(16)-C(17)-F(8) -65.34(18) O(2)-C(16)-C(18)-F(10) -71.01(17) C(15)-C(16)-C(18)-F(10) 50.62(18) C(17)-C(16)-C(18)-F(10) 170.90(13)Supplementary information
doi: 10.1038/nchem.513 O(2)-C(16)-C(18)-F(12) 47.99(18) C(15)-C(16)-C(18)-F(12) 169.61(13) C(17)-C(16)-C(18)-F(12) -70.11(17) O(2)-C(16)-C(18)-F(11) 167.84(13) C(15)-C(16)-C(18)-F(11) -70.53(18) C(17)-C(16)-C(18)-F(11) 49.74(18) C(15)-C(16)-O(2)-Si(2) 12.59(16) C(18)-C(16)-O(2)-Si(2) 135.23(11) C(17)-C(16)-O(2)-Si(2) -106.00(12) C(10)#1-Si(2)-O(2)-C(16) 117.08(11) C(10)-Si(2)-O(2)-C(16) -7.51(11) Si(1)-Si(2)-O(2)-C(16) -124.99(10) C(21)-N(1)-C(22)-C(23) 58.4(2) C(20)-N(1)-C(22)-C(23) -63.9(2) C(19)-N(1)-C(22)-C(23) 176.90(18) N(1)-C(22)-C(23)-C(28) -94.0(2) N(1)-C(22)-C(23)-C(24) 89.9(2) C(28)-C(23)-C(24)-C(25) 1.0(3) C(22)-C(23)-C(24)-C(25) 177.13(19) C(23)-C(24)-C(25)-C(26) -0.7(3) C(24)-C(25)-C(26)-C(27) 0.1(3) C(25)-C(26)-C(27)-C(28) 0.1(3) C(26)-C(27)-C(28)-C(23) 0.3(3) C(24)-C(23)-C(28)-C(27) -0.8(3) C(22)-C(23)-C(28)-C(27) -177.00(17)Supplementary information
doi: 10.1038/nchem.513Theoretical calculation of disilicate 2d, disilanes 3 and 4, and anion radical 5.
Geometries of the disilicate 2d, the dianion part of 2, disilanes 3 and 4, and the corresponding anion radical 5 were fully optimized with density functional theory (DFT) at the B3PW914-6 levels using the GAUSSIAN 03 suite of programs.7 As the basis sets, 6-311+G(2d) for Si, 6-31G(d) for C, H, O, and F were employed as supplied with Gaussian 03 for the B3PW91 calculations. The transition energies were obtained by time-dependent DFT calculations of 2d at the same level as the geometry optimization. Cartesian coordinates in optimized geometries of the disilicate 2d, the dianion part of 2, disilanes 3 and 4, and anion radical 5 are shown in Supplementary Tables 6-10. The optimized structures of 2d, 2, 3, 4 and 5 are shown in Supplementary Figures 21-25.
Supplementary information
doi: 10.1038/nchem.513Supplementary Table 6. Cartesian coordinates in optimized geometry of the disilicate 2d. Atomic Coordinates (Angstroms)
Number X Y Z 6 -0.861838 1.509908 -2.061387 6 0.576578 1.390885 2.339778 6 1.872150 1.662098 2.791666 6 2.146275 2.775121 3.582714 6 1.117639 3.642993 3.947545 6 -0.184763 3.387995 3.527107 6 -0.437659 2.271566 2.727340 6 -1.817533 1.842026 2.232621 6 -2.703729 1.484684 3.461318 6 -2.493806 2.977360 1.419908 6 0.862836 -1.247237 -2.229813 6 -0.578823 -1.664374 2.152671 6 -1.874842 -1.988867 2.566800 6 -2.149521 -3.190039 3.216091 6 -1.121022 -4.095712 3.473467 6 0.181689 -3.791158 3.088564 6 0.435139 -2.585729 2.430899 6 1.815620 -2.099144 1.994185 6 2.700419 -1.894925 3.258395 6 2.493310 -3.126484 1.049741 6 4.240760 0.639321 0.276738 6 -4.241750 -0.665177 0.194454 6 -2.198532 1.580603 -2.463022 6 2.199228 -1.268250 -2.638022 6 6.352520 -0.417256 0.920310 6 5.538774 -0.626084 -1.371426 6 6.352776 1.527605 -0.569249
Supplementary information
doi: 10.1038/nchem.513 6 -5.534761 0.791578 -1.291777 6 -6.352518 -1.442261 -0.757666 6 -2.695265 2.687763 -3.145644 6 2.696184 -2.285369 -3.448614 6 -1.850992 3.755791 -3.448755 6 1.852457 -3.310137 -3.876773 6 -0.513229 3.709717 -3.066950 6 0.514983 -3.311140 -3.491226 6 -0.037766 2.594476 -2.372886 6 0.039333 -2.287450 -2.668237 6 1.404150 2.396857 -1.907292 6 -1.402288 -2.148726 -2.180860 6 2.336630 2.339505 -3.151487 6 -2.336601 -1.946540 -3.408504 6 1.847741 3.565526 -0.984522 6 -1.842919 -3.418860 -1.401838 9 1.904755 1.434412 -4.034132 9 -1.754447 3.319334 0.369796 9 -2.732038 4.094798 2.133572 9 -3.713887 2.584134 0.938141 9 -1.910400 -0.939829 -4.176321 9 1.754420 -3.339204 -0.034279 9 2.733198 -4.322042 1.622206 9 3.712977 -2.675925 0.619997 9 2.452440 3.513351 -3.799539 9 -2.447274 -3.034310 -4.193244 9 3.609815 1.972102 -2.811760 9 -3.611235 -1.629136 -3.026429 9 1.070440 3.633225 0.094156 9 -1.065564 -3.610509 -0.338190Supplementary information
doi: 10.1038/nchem.513 9 1.809658 4.772527 -1.588248 9 -1.801572 -4.546604 -2.142969 9 3.125899 3.405798 -0.555579 9 -3.121464 -3.313809 -0.957486 9 -2.088181 0.596952 4.248264 9 2.082307 -1.113630 4.149362 9 -3.022334 2.548447 4.225163 9 3.022198 -3.044440 3.884367 9 -3.884718 0.923139 3.084368 9 3.879716 -1.287487 2.954411 1 -2.838640 0.734444 -2.248160 1 2.838873 -0.453374 -2.323818 1 4.335581 1.368635 1.081312 1 3.675197 1.068714 -0.547660 1 7.363849 -0.662837 0.587956 1 6.390566 0.245414 1.786420 1 5.800326 -1.319994 1.179839 1 4.927015 -1.488429 -1.106775 1 5.068651 -0.076248 -2.186602 1 6.546785 -0.938701 -1.654295 1 5.763053 2.049543 -1.323875 1 6.456679 2.160087 0.314141 1 -4.339017 -1.485310 0.905914 1 -3.674586 -0.993907 -0.673972 1 -7.364827 0.592231 0.653987 1 -6.393778 -0.454000 1.736069 1 -5.802479 1.172929 1.323707 1 -4.920138 1.613547 -0.924953 1 -5.066502 0.342869 -2.167670 1 -6.541695 1.139337 -1.534667Supplementary information
doi: 10.1038/nchem.513 1 -5.761138 -1.870074 -1.568170 1 -6.459381 -2.176377 0.042836 1 -3.738068 2.719900 -3.458952 1 3.738796 -2.278954 -3.764120 1 7.338168 1.266889 -0.962477 1 -7.336516 -1.134702 -1.119270 1 -2.229921 4.621151 -3.987574 1 2.231586 -4.104425 -4.515618 1 0.143884 4.536975 -3.310846 1 -0.141888 -4.103604 -3.831969 1 2.665533 0.970804 2.536864 1 -2.668404 -1.272080 2.397069 1 3.161609 2.964772 3.926824 1 -3.165146 -3.420396 3.533455 1 1.324848 4.512117 4.567637 1 -1.328577 -5.033963 3.982822 1 -0.986511 4.054296 3.826566 1 0.983363 -4.488680 3.305695 1 3.717070 -0.248461 0.629932 1 -3.718020 0.173473 0.652316 7 5.627726 0.279975 -0.184239 7 -5.627313 -0.251234 -0.222977 8 1.517572 1.221344 -1.209411 8 -1.516305 -1.064541 -1.348219 8 -1.708050 0.741633 1.421093 8 1.706948 -0.908007 1.322719 14 0.000613 0.070719 -1.151632 14 -0.000641 -0.076691 1.264156Supplementary information
doi: 10.1038/nchem.513Supplementary Figure 22. Optimized structure of the dianion part of the disilicate 2. Supplementary Table 7. Cartesian coordinates in optimized geometry of the dianion part of disilicate 2.
Atomic Coordinates (Angstroms) Number X Y Z 14 0.000001 1.196830 0.000001 8 -0.974067 1.352235 1.591720 9 -0.883366 4.157119 1.879742 9 -2.932245 4.198461 2.572835 9 -1.435330 3.107538 3.692045 6 -1.485965 2.126562 -0.767143 9 -3.570531 0.260677 1.455159 6 -1.702813 2.417009 -2.119384 9 -4.387983 2.020406 2.415421 6 -2.845218 3.101336 -2.528593 9 -2.908235 0.820969 3.439727 6 -3.789248 3.516485 -1.587511 6 -3.596024 3.235836 -0.236880
Supplementary information
doi: 10.1038/nchem.513 6 -2.453588 2.533393 0.154672 6 -2.099976 2.125635 1.588430 6 -1.840473 3.400510 2.440034 6 -3.246153 1.298888 2.229186 6 1.485970 2.126559 0.767145 6 1.702823 2.416997 2.119387 6 2.845227 3.101324 2.528595 6 3.789253 3.516482 1.587512 6 3.596024 3.235841 0.236880 6 2.453588 2.533397 -0.154672 6 2.099973 2.125643 -1.588430 6 1.840456 3.400520 -2.440028 9 0.883348 4.157121 -1.879727 9 2.932223 4.198477 -2.572834 9 1.435305 3.107549 -3.692036 6 3.246153 1.298908 -2.229195 9 3.570547 0.260700 -1.455170 9 4.387974 2.020437 -2.415438 9 2.908231 0.820986 -3.439733 8 0.974069 1.352237 -1.591719 1 -0.962851 2.096599 -2.845382 1 -3.004257 3.311054 -3.585881 1 -4.681659 4.054744 -1.905437 1 -4.332931 3.552474 0.494491 1 0.962866 2.096582 2.845386 1 3.004271 3.311037 3.585884 1 4.681664 4.054742 1.905437 1 4.332927 3.552484 -0.494492 14 -0.000001 -1.196830 0.000001 8 0.974067 -1.352235 1.591720Supplementary information
doi: 10.1038/nchem.513 9 0.883366 -4.157119 1.879742 9 2.932245 -4.198461 2.572835 9 1.435330 -3.107538 3.692045 6 1.485965 -2.126562 -0.767143 9 3.570531 -0.260677 1.455159 6 1.702813 -2.417009 -2.119384 9 4.387983 -2.020406 2.415421 6 2.845218 -3.101336 -2.528593 9 2.908235 -0.820969 3.439727 6 3.789248 -3.516485 -1.587511 6 3.596024 -3.235836 -0.236880 6 2.453588 -2.533393 0.154672 6 2.099976 -2.125635 1.588430 6 1.840473 -3.400510 2.440034 6 3.246153 -1.298888 2.229186 6 -1.485970 -2.126559 0.767145 6 -1.702823 -2.416997 2.119387 6 -2.845227 -3.101324 2.528595 6 -3.789253 -3.516482 1.587512 6 -3.596024 -3.235841 0.236880 6 -2.453588 -2.533397 -0.154672 6 -2.099973 -2.125643 -1.588430 6 -1.840456 -3.400520 -2.440028 9 -0.883348 -4.157121 -1.879727 9 -2.932223 -4.198477 -2.572834 9 -1.435305 -3.107549 -3.692036 6 -3.246153 -1.298908 -2.229195 9 -3.570547 -0.260700 -1.455170 9 -4.387974 -2.020437 -2.415438 9 -2.908231 -0.820986 -3.439733Supplementary information
doi: 10.1038/nchem.513 8 -0.974069 -1.352237 -1.591719 1 0.962851 -2.096599 -2.845382 1 3.004257 -3.311054 -3.585881 1 4.681659 -4.054744 -1.905437 1 4.332931 -3.552474 0.494491 1 -0.962866 -2.096582 2.845386 1 -3.004271 -3.311037 3.585884 1 -4.681664 -4.054742 1.905437 1 -4.332927 -3.552484 -0.494492Supplementary Figure 23. Optimized structure of the disilane 3.
Supplementary Table 8. Cartesian coordinates in optimized geometry of disilane 3. Atomic Coordinates (Angstroms)
Number X Y Z 14 0.180973 -1.195162 0.078735 14 -0.181523 1.195652 0.078052
Supplementary information
doi: 10.1038/nchem.513 8 -2.069387 -1.288766 -0.200435 8 1.928451 -1.250218 0.294882 8 2.067675 1.289549 -0.201174 8 -1.928863 1.251221 0.294189 6 -0.011259 -2.128545 -1.558137 6 1.123664 -2.553063 -2.265238 6 1.018159 -3.269733 -3.454318 6 -0.236720 -3.587778 -3.963953 6 -1.381898 -3.180026 -3.286443 6 -1.268385 -2.451934 -2.100634 6 -2.504473 -1.975187 -1.353939 6 -3.360642 -3.163121 -0.833906 9 -2.597096 -3.974455 -0.092993 9 -3.889003 -3.890015 -1.829057 9 -4.367562 -2.724204 -0.065202 6 -3.353046 -1.014009 -2.225452 9 -2.564875 -0.088261 -2.788418 9 -4.003332 -1.654297 -3.203085 9 -4.262946 -0.369892 -1.476258 6 -0.024489 -2.170038 1.671195 6 -1.167119 -2.582690 2.365107 6 -1.052689 -3.336325 3.530426 6 0.203926 -3.697691 4.014514 6 1.355407 -3.300484 3.340363 6 1.231215 -2.533912 2.181531 6 2.409081 -2.035008 1.356215 6 3.200301 -3.221820 0.744571 9 2.359823 -4.054565 0.113324 9 3.849660 -3.932286 1.680771 9 4.105854 -2.798969 -0.149911Supplementary information
doi: 10.1038/nchem.513 6 3.339869 -1.125098 2.195255 9 2.622364 -0.138768 2.754005 9 4.281595 -0.553070 1.426382 9 3.963805 -1.785765 3.179830 6 0.011489 2.129062 -1.558818 6 -1.123290 2.554314 -2.265753 6 -1.017515 3.271135 -3.454713 6 0.237441 3.588619 -3.964466 6 1.382511 3.180117 -3.287260 6 1.268740 2.451935 -2.101533 6 2.504303 1.973923 -1.355091 6 3.362826 3.160694 -0.836139 9 2.600924 3.974133 -0.095842 9 3.892572 3.885791 -1.831867 9 4.368931 2.720493 -0.067082 6 3.350720 1.010125 -2.225861 9 2.560720 0.084566 -2.786502 9 4.260355 0.365910 -1.476408 9 4.001080 1.647782 -3.205186 6 0.024542 2.170944 1.670119 6 1.167303 2.583540 2.363825 6 1.053116 3.337819 3.528754 6 -0.203381 3.699903 4.012619 6 -1.355001 3.302760 3.338663 6 -1.231069 2.535530 2.180239 6 -2.409193 2.036562 1.355257 6 -3.200154 3.223312 0.743097 9 -2.359604 4.055188 0.110801 9 -3.848752 3.934803 1.679051 9 -4.106297 2.800206 -0.150650Supplementary information
doi: 10.1038/nchem.513 6 -3.340072 1.127268 2.194910 9 -2.622813 0.140550 2.753306 9 -3.963040 1.788282 3.179852 9 -4.282571 0.555767 1.426600 1 -2.443372 -0.378447 -0.079945 1 2.440216 0.378892 -0.079226 1 2.106954 -2.317959 -1.877778 1 1.917866 -3.581814 -3.978161 1 -0.330994 -4.151313 -4.888271 1 -2.357283 -3.429637 -3.687580 1 -2.149345 -2.314969 1.997600 1 -1.948969 -3.646471 4.061501 1 0.290452 -4.290853 4.921070 1 2.330508 -3.585836 3.718820 1 -2.106690 2.319623 -1.878302 1 -1.917123 3.583739 -3.978414 1 0.331863 4.152282 -4.888691 1 2.357966 3.429258 -3.688491 1 2.149427 2.315295 1.996459 1 1.949497 3.647920 4.059687 1 -0.289704 4.293574 4.918862 1 -2.330001 3.588667 3.716965Supplementary information
doi: 10.1038/nchem.513Supplementary Figure 24. Optimized structure of the disilane 4.
Supplementary Table 9. Cartesian coordinates in optimized geometry of disilane 4. Atomic Coordinates (Angstroms)
Number X Y Z 14 0.993174 -0.139805 0.658434 14 -0.990392 -0.058545 -0.659712 6 2.024021 -1.626678 0.071412 6 1.651864 -2.937764 0.430174 6 3.166144 -1.472631 -0.734864 6 2.386856 -4.044267 0.001713 1 0.775375 -3.102676 1.052676 6 3.905042 -2.576720 -1.165903 1 3.489602 -0.475790 -1.023433 6 3.516800 -3.865873 -0.799114 1 2.079508 -5.045094 0.295364 1 4.786435 -2.428962 -1.785255 1 4.091774 -4.726071 -1.132553
Supplementary information
doi: 10.1038/nchem.513 6 2.017165 1.448234 0.479590 6 2.683489 2.007887 1.585288 6 2.147299 2.109081 -0.756844 6 3.447191 3.170431 1.463347 1 2.608968 1.531398 2.559746 6 2.911645 3.269662 -0.887193 1 1.642554 1.715542 -1.636453 6 3.563459 3.804106 0.225477 1 3.950880 3.581374 2.334877 1 2.993673 3.759259 -1.854360 1 4.156062 4.710180 0.128717 6 -2.149934 -1.448447 -0.073428 6 -1.972887 -2.773849 -0.516312 6 -3.198141 -1.200844 0.832611 6 -2.802445 -3.805498 -0.072619 1 -1.179001 -3.009339 -1.221084 6 -4.029786 -2.229126 1.280286 1 -3.378071 -0.187644 1.183600 6 -3.833170 -3.535271 0.829328 1 -2.646651 -4.819057 -0.434207 1 -4.835073 -2.009288 1.977044 1 -4.481394 -4.336587 1.174862 6 -1.881743 1.608435 -0.484807 6 -2.519889 2.200504 -1.590760 6 -1.945855 2.294298 0.742501 6 -3.195792 3.416699 -1.476659 1 -2.491643 1.707817 -2.559619 6 -2.622820 3.509122 0.865147 1 -1.457172 1.878837 1.621090 6 -3.249814 4.073826 -0.246504Supplementary information
doi: 10.1038/nchem.513 1 -3.679537 3.851393 -2.347950 1 -2.654926 4.017165 1.825736 1 -3.773971 5.021726 -0.155535 6 0.559476 -0.404355 2.491326 1 1.456316 -0.616922 3.084817 1 0.069892 0.476717 2.922084 1 -0.125981 -1.250835 2.607937 6 -0.574793 -0.357824 -2.490881 1 0.048926 -1.250253 -2.609712 1 -1.482872 -0.502689 -3.087708 1 -0.022914 0.487865 -2.916679Supplementary information
doi: 10.1038/nchem.513Supplementary Table 10. Cartesian coordinates in optimized geometry of the anion radical 5.
Atomic Coordinates (Angstroms)
Number X Y Z 7 0.893652 3.809277 -0.693211 6 -0.505296 3.644926 -0.179757 6 1.862223 3.405027 0.381042 6 1.082696 2.928983 -1.895521 6 1.125420 5.233042 -1.070386 1 -0.642860 2.608378 0.135422 1 -0.647614 4.322095 0.664888 1 -1.206237 3.882658 -0.980824 1 2.873905 3.611263 0.029089 1 1.645709 3.992793 1.275547 1 1.749434 2.331205 0.565377 1 0.784747 1.906479 -1.627414 1 0.450973 3.307465 -2.701616 1 2.133908 2.952274 -2.184516 1 0.389365 5.528462 -1.820802 1 1.021503 5.858862 -0.181363 1 2.132926 5.331306 -1.479182 8 -1.716189 -0.769580 -0.985500 14 -0.142369 -0.350079 -0.264757 8 1.506928 0.319555 0.232722 9 2.611878 -1.010994 2.424426 9 -3.055755 -2.571829 0.639313 9 -4.892643 -1.423682 0.497568 9 4.518268 -1.189776 1.402667 9 -3.988285 -2.252086 -1.287541 9 3.671866 0.766064 1.791286
Supplementary information
doi: 10.1038/nchem.513 6 0.703077 -2.009498 -0.433179 9 2.777826 -0.012846 -2.207931 6 -1.058736 0.206543 1.274334 9 -4.762476 1.046439 -0.555234 6 0.129457 -3.241370 -0.772581 9 4.580842 -0.745223 -1.251723 6 -0.561762 0.697805 2.490382 9 -3.880369 0.229294 -2.354784 6 0.921546 -4.382238 -0.873078 9 3.874929 1.261973 -0.848394 6 -1.433571 1.132035 3.486507 6 2.297480 -4.305421 -0.647822 6 -2.814189 1.093249 3.277456 6 -3.329374 0.608518 2.075045 6 2.889696 -3.086105 -0.323142 6 2.086496 -1.950560 -0.217950 6 -2.449278 0.168098 1.086750 6 2.584715 -0.540654 0.101392 6 -2.846493 -0.399686 -0.279857 6 3.362005 -0.499852 1.438902 6 -3.713994 -1.673923 -0.110428 6 -3.601738 0.659376 -1.120408 6 3.471412 -0.016674 -1.057061 1 0.511705 0.713124 2.657905 1 -0.939859 -3.298671 -0.951094 1 0.467775 -5.337249 -1.128304 1 -1.040119 1.494430 4.434221 1 2.914147 -5.197356 -0.727758 1 -3.493892 1.431612 4.055836 1 3.960115 -3.032259 -0.155083Supplementary information
doi: 10.1038/nchem.5131 -4.402487 0.572093 1.921953
Complete List of the Authors of the Reference
Complete list of the authors of reference 12, 17 and 20 of the main text is shown below. The authors of the reference 23 of the main text is shown in reference 7 of this Supporting Information.
Ref. 12. El-Sayed, I., Hatanaka, Y., Muguruma, C., Shimada, S., Tanaka, M., Koga, N., & Mikami, M. Synthesis, X-ray structure, and electronic properties of oligosilanes containing pentacoordinate silicon moieties at internal positions. J. Am. Chem. Soc. 121, 5095-5096 (1999).
Ref. 17 Kano, N., Nakagawa, N., Shinozaki, Y., Kawashima, T., Sato, Y., Naruse, Y. & Inagaki, S. Disilanes containing two high-coordinate silicon atoms bridged by carboxylate ligands: synthesis, structure, and dynamic behavior. Organometallics 24, 2823-2826 (2005).
Ref. 20 Knopf, C. Herzog, U., Roewer, G., Brendler, E., Rheinwald, G. & Lang, H. Interactions of chloromethyldisilanes with tetrakis(dimethylamino)ethylene (TDAE), formation of [TDAE]+·[Si
3Me2Cl7]–. J. Organomet. Chem. 662, 14-22 (2002).
References
1. Perozzi, E. F. & Martin, J. C. Facile syntheses of isolable organic derivatives of hypervalent sulfur, phosphorus, and silicon. Introduction of a stabilizing bidentate ligand via its dilithio derivative. J. Am. Chem. Soc. 101, 1591-1593 (1979).
2. Rigaku, CrystalClear, Rigaku Corp., 2000.
3. Sheldrick, G. M. SHELX-97, Program for the refinement of crystal structures, University of Göttingen: Göttingen, Germany, 1997.
4. Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098-3100 (1988).
5. Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J.
Chem. Phys. 98, 5648-5652 (1993).
Supplementary information
doi: 10.1038/nchem.513electron-gas correlation energy. Phys. Rev. B 45, 13244-13249 (1992).
7. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C. & Pople, J. A. Gaussian 03, revision C. 01, Gaussian, Inc.: Wallingford, CT, 2004.
