The diorgano(bismuth)alcoholate [Bi((C6H4CH2)2S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi-O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO =(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed-shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations

Andreas Stoy

Crispin Lichtenberg

Jacqueline Ramler

Johannes Schwarzmann

German

Ramler, Jacqueline

Publikations- und Dokumentenserver der Universitätsbibliothek Marburg

European Journal ofInorganic ChemistrySupporting InformationTwo Faces of the Bi  O Bond: Photochemically andThermally Induced Dehydrocoupling for Si  O BondFormationJacqueline Ramler, Johannes Schwarzmann, Andreas Stoy, and Crispin Lichtenberg*Wiley VCH Dienstag, 22.02.20222207 / 229865 [S. 23/23] 1        Table of Contents  Experimental……………………………………………………………………………. S02 DFT calculations………………………………………………………………………... S05 EPR spectroscopy․……………………………………………..………………………․․ S05 Energies of compounds investigated by DFT calculations……………………………... S05 IR spectroscopy……………………………………………………………………….… S06 NMR spectra ……………………..…………………………․․..……………………….. S07 Cartesian coordinates of 1-OPh……………………..…………………………․․..…......S08 References………………………………………………………………………………. S09 S2  Experimental General considerations. All air- and moisture-sensitive manipulations were carried out using standard vacuum line Schlenk techniques or in gloveboxes containing an atmosphere of purified argon. Solvents were degassed and purified according to standard laboratory procedures. NMR spectra were recorded on Bruker instruments operating at 400 or 500 MHz with respect to 1H. 1H and 13C NMR chemical shifts are reported relative to SiMe4 using the residual 1H and 13C chemical shifts of the solvent as a secondary standard. NMR spectra were recorded at ambient temperature (typically 25 °C), if not otherwise noted. UV-vis spectra were recorded in acetonitrile solution at 23 °C with a an Analytik Jena Specord S600 spectrometer using the WinASPECT software and an UNISOKU CoolSpeK Cryostat. Elemental analyses were performed on a Vario Micro Cube by Elementar Analysesysteme GmbH. Mass spectrometric analyses were performed with an Exactive Plus instrument (Thermo Scientific). Single crystals suitable for X-ray diffraction were coated with perfluorinated polyether oil in a glovebox, transferred to a nylon loop and then transferred to the goniometer of a diffractometer equipped with a molybdenum X-ray tube (λ = 0.71073 Å). The structures were solved using intrinsic phasing methods (SHELXT) completed by Fourier synthesis and refined by full-matrix least-squares procedures. CCDC 2115890 contains the crystallographic information for this work. Photochemical experiments were performed using a mercury-vapor lamp (I = 19 A, U = 26 V) and regular borosilicate glassware.   Synthesis of 1-OPh The assignment of 1H and 13C NMR spectroscopic resonances of compound 1-OPh was performed according to the labelling scheme shown in Figure S1.   Figure S1. Labelling scheme for assignment of 1H and 13C NMR spectroscopic resonances of compounds 1-OPh (X = OPh).  [(қ2-C14H12S)Bi(OPh)] (1-OPh).  Phenol (47.1 mg, 0.50 mmol) was added to a suspension of sodium hydride                                             (12.0 mg, 0.50 mmol) in THF (1 mL) at 0 °C. The reaction mixture was stirred at 0 °C for 1 h, then for a further 45 min at ambient temperature. A solution of precursor [(C14H12S)BiCl][1] (212 mg, 0.45 mmol) in THF (5 mL) was added dropwise at –78 °C. The suspension was stirred at –78 °C for 20 min, then at ambient temperature for 1 h 25 min. All volatiles were removed under reduced pressure and the residue was extracted with a benzene/THF (1:0.5, 2 × 3 mL) mixture and filtered. The filtrate was layered with n-pentane (6 mL). The product was obtained after 16 h at ambient temperature, isolated by filtration and dried in vacuo as colorless crystals. Yield: 189 mg, 0.36 mmol, 79%.  1H NMR (500 MHz, C6D6): δ = 3.45 (d, 2H, 2JHH = 15.4 Hz, CH2), 3.55 (d, 2H, 2JHH = 15.4 Hz, CH2), 6.91 – 7.02 (m, 5H, para-C6H5, H-4, H-8, H-3, H-9), 7.17 (m, 2H, ortho-C6H5, overlap S3  with solvent resonance), 7.27 (ddd, 2H, 4JHH = 1.5 Hz, 3JHH = 7.0 Hz, 3JHH = 7.0 Hz, H-2, H-10), 7.39 (m, 2H, meta-C6H5), 8.80 (d, 2H, 3JHH = 7.6 Hz, H-1, H-11) ppm. 13C{1H} NMR (125.8 MHz, C6D6): δ = 40.3 (s, CH2), 117.9 (s, para-C6H5), 121.1 (s, ortho-C6H5), 128.4 (s, C-3, C-9), 130.0 (s, meta-C6H5), 130.2 (s, C-2, C-10), 131.0 (s, C-4, C-8), 137.4 (s, C-1, C-11), 146.7 (s, C-4a, C-7a), 166.0 (s, ipso-C6H4), 176.8 (br, C-11a, C-12a) ppm. Elemental analysis: Anal. calc. for: [C20H17BiSO] (514.39 g/mol): C 46.70, H 3.33, S 6.23; found: C 46.87, H 3.44, S, 6.27.   [Bi(C6H4CH2)2S]2 (3). Compound 3 has previously been synthesized following a different synthetic route.[2] In this work, the following protocol was applied: A solution of PhSiH3 (4.20 mg, 4.78 µL, 38.80 µmol) and [Bi(C6H4CH2)2S(OPh)] (1-OPh) (20.0 mg, 38.8 µmol) in benzene-d6 (0.5 mL) was heated to 60 °C for 1 d. The red crystalline product precipitated, was isolated by filtration, and dried in vacuo. Yield: 16.4 mg, 19. 4 µmol, quant. The product was identified by single-crystal X-ray diffraction analysis of several samples.[2]  Analytical data for P1-P3 and P5 were taken from the literature (P1, P1’, P1’’: ref. [2-3], P2, P2’: ref. [2], P3, P3’: ref. [2-3], P5: ref. [4], P5’: ref. [5]).  Compounds P4, P4’ and P4’’ were unambiguously identified from the reaction mixture by high-resolution mass spectrometry and characteristic resonances were assigned by careful analysis of one- and two-dimensional NMR spectra and comparison with the literature (ref. [2-5]). P4.  1H NMR (400 MHz, C6D6): δ = 5.34 (s, 2H, Si-H), 7.54 (m, 2H, ortho-SiPh) ppm.  HR-ASAP-MS (THF): positive mode (%): found m/z = 199.0570 (10); calculated for [C12H11OSi]+, m/z = 199.0574.  P4’. 1H NMR (400 MHz, C6D6): δ = 5.61 (s, 1H, Si-H), 7.74 (m, 2H ortho-SiPh) ppm.  HR-LIFDI-MS (THF): positive mode (%): found m/z = 292.0908 (10), calculated for [C18H16O2Si]+, m/z = 292.0914.  P4’’. 1H NMR (400 MHz, C6D6): δ = 6.77 (m, 6H, meta-OPh), 6.98 (m, 6H, ortho-OPh), 7.04 (m, 1H, para-SiPh), 7.08 (m, 2H, meta-SiPh), 7.13 (m, 3H, para-OPh), 7.89 (m, 2H, ortho-SiPh) ppm.  13C NMR (100 MHz, C6D6): δ = 119.92 (s, para-OPh), 122.75 (s, meta-OPh), 128.30 (s, meta-SiPh), 128.48 (s, Si-C), 129.73 (s, ortho-OPh), 131.44 (s, para-SiPh), 135,09 (s, ortho-SiPh), 153.50 (s, ipso-OPh) ppm.  HR-LIFDI-MS (THF): positive mode (%), found m/z = 384.1167 (100) calculated for [C24H20O3Si]+, m/z = 384.1176.  HR-ASAP-MS (THF): positive mode (%), found m/z = 385.1241 (58) calculated for [C24H21O3Si]+, m/z = 385.1254. S4  General procedure for catalytic coupling of TEMPO or phenol with silanes. In a J. Young-NMR tube, the substrate (typically 0.09 mmol) was dissolved in benzene-d6 (0.5 mL). The desired amount (typically 10 mol%) of the selected catalyst and TEMPO or phenol (one or two equivalents, see Tables 2 and 3 in the main text) were added and the chosen reaction conditions were applied for the time noted in Tables 2 and 3 in the main text. The conversion of TEMPO/phenol is given in these tables and was determined through NMR spectroscopic quantification of the silanes S1-S3 and P1-P5 in the reaction mixture.  The reaction conditions used were either a photochemical set-up (constant irradiation with a mercury-vapor lamp at 23 °C (conditions: h∙ν)) or the reaction was kept under ambient light at 80 °C (thermal approach) and are noted in Tables 2 and 3 in the main text.  The conversion given in Tables 2 and 3 is the conversion of TEMPO and phenol, respectively, as determined by 1H NMR spectroscopy. The conversion of TEMPO was determined indirectly by determining the formation of singly and doubly substituted products (e.g. P1 and P1’) and the amount of remaining starting material (e.g. S1). Due to the presence of two OTEMP groups in doubly substituted products, the formation of one equivalent of such a species corresponds to the conversion of two equivalents of TEMPO. Thus, a molar ratio of S1 : P1 : P1’ of, for example, 1.0 : 1.0 : 1.0 would translate into a conversion of 75% (25% P1 and 25% P1’), if one equivalent of TEMPO was used, and 37.5% (12.5% P1 and 12.5% P1’), if two equivalents of TEMPO were used.  During the reactions, small amounts of a black precipitate may be observed, which is commonly associated with the formation of low-valent bismuth species (“bismuth black”). These reactions are likely to be responsible for de-activation processes of catalytically active species.  If the reaction was conducted in silanized NMR tubes, the silanization of the reaction vessel was carried out prior to use. To this end, approximately 1.0 mL of hexamethyldisilazane (HMDS) were heated with a heat gun in the J. Young-NMR tube, followed by evaporation of all volatiles.  Mass spectrometric analysis of catalytic reaction An aliquot of a reaction performed under the conditions described in Table 2, entry 2 in the main part was analysed by high-resolution mass spectrometry. HR-ASAP-MS (THF): positive mode (%): found: m/z = 158.1536 (35); calculated for [C9H20NO]+, m/z = 158.1539; found: m/z = 421.0446 (<5); calculated for [C14H12BiS]+, m/z = 421.0458. The signal for [TEMPOH∙H]+ (calc. m/z = 158.1539) was also detected, when an authentic sample of TEMPOH was analyzed under identical conditions, but was not detected, when an authentic sample of TEMPO was analysed under identical conditions. HR-ASAP of TEMPO: HR-ASAP-MS (THF): positive mode (%): found: m/z = 142.1224 (100); calculated for [C8H17NO]+ m/z = 142.1226; found: m/z = 157.1459 (30); calculated for [C9H19NO]+ m/z = 157.1461; found m/z = 156.1381 (20); calculated for [C9H18NO]+, m/z = 156.1383.   S5  DFT Calculations DFT calculations were performed with the Gaussian program (rev. b.01)[6] using the 6-31G(d,p)[7] [H, C, N, O, S) or the LANL2DZ[8] [Bi] basis sets and the B3LYP functional.[9] The D3 version of Grimme’s dispersion model with the original D3 damping function was applied.[10] Frequency analysis of the reported structure showed no imaginary frequencies for the ground state. Thermodynamic parameters were calculated at a temperature of 298.15 K and a pressure of 1.00 atm. NBO analyses were performed using the programme version NBO 7.[11] TD-DFT studies were performed with the Gaussian program (rev. b.01),[6] the functional CAM-B3LYP[12], and with Grimme D3 dispersion corrections on compound 1-OPh.[10]  Second order perturbation analysis for 1-OPh revealed two n(S)→p(Bi) interactions as well as one n(O1)→p(Bi) interaction. In order to quantify these Bi∙∙∙E interactions between the bismuth atom and the sulphur atom of the ligand backbone and the oxygen of the phenolate group, respectively, deletion energies were determined. Deleting the specific Fock matrix elements related to these interactions gave deletion energies of 21.7 kcal∙mol–1 for the sum of n(S)→p(Bi) interactions and 92.1 kcal∙mol–1 for the n(O1)→p(Bi) interaction in 1-OPh.  The natural charges for compounds 1-EPh (E = S, Se, Te) that are reported in the main part were obtained from geometry-optimized structures of these species as reported in ref. [2].  Energies of Compounds Investigated by DFT Calculations The energies of compound 1-OPh investigated by DFT calculations are given in Table S1. Its Cartesian coordinates are given at the end of the document. Table S1. Energies of calculated species 1-OPh. Entry Compound ΔH [hartree] ΔG [hartree] 1 1-OPh –1250.941959 –1251.014963   EPR Spectroscopy EPR spectra at X-band (9.47 GHz) were measured on a Bruker Magnettech ESR5000 spectrometer with an TCH04 Temperature Controller set to 80 °C, using 1 mW of microwave power and 0.2 mT of field modulation at 100 kHz. The spectra were recorded with a sweep time of 240 s from 200 to 400 mT field range, over a time period of 19 h with 1 h time intervals.   S6  Infra-Red Spectroscopy  Figure S2. Stack-plot of solid-state IR spectra. Black: reaction mixture (catalytic conditions, see main text). Dark green: 2,2,6,6-tetramethylpiperidine. Green: TEMPO. Blue: 1:1 mixture of TEMPO and 2,2,6,6-tetramethylpiperidine. Red: TEMPOH. Orange: 1:1 mixture of TEMPO and TEMPOH. S7  NMR Spectra of 1-OPh Figure S3. 1H and 13C NMR spectra of [(қ2-C14H12S)Bi(OPh)] (1-OPh) in benzene-d6.  S8   Figure S4. Stack-plot of 1H NMR spectra in C6D6. Black: TEMPOH. Blue: TEMPO. Violet: 2,2,6,6-tetramethylpiperidine. Green: 1:1 mixture of TEMPO and TEMPOH. Dark green: 1:1 mixture of TEMPO and 2,2,6,6-tetramethylpiperidine. Red: reaction mixture under catalytic conditions (see main text).   S9  Cartesian Coordinates of 1-OPh Atom X Y Z Bi -0.1097810 0.2032670 -0.8171930 S 2.6870070 -0.5901560 -1.6353990 O -1.6339460 0.7784940 0.5627890 C -2.9334380 0.4844680 0.3297940 C 1.2603420 1.5907990 0.2916230 C 1.4897090 3.7130340 1.4603120 H 1.0327280 4.6030710 1.8840720 C 0.6920970 2.7435690 0.8468530 H -0.3860810 2.8701000 0.8177080 C 0.4226940 -1.5898800 0.4507110 C 3.4449840 2.3843580 0.9798730 H 4.5214630 2.2411920 1.0418370 C 2.8715080 3.5370190 1.5168000 H 3.5037030 4.2905090 1.9779260 C -0.3008580 -1.7961240 1.6303550 H -1.0911470 -1.0993930 1.8941600 C 2.2878480 -2.3300190 -1.1468830 H 1.7443710 -2.7134750 -2.0187350 H 3.2201320 -2.8962040 -1.0747870 C -3.3627820 -0.8004610 -0.0553260 H -2.6316930 -1.5980670 -0.1604140 C 2.6519980 1.3975400 0.3771890 C 0.0015840 -2.8646080 2.4790920 H -0.5669270 -3.0076050 3.3938910 C 1.4708420 -2.4696550 0.1226040 C 3.3328140 0.1122620 -0.0498500 H 3.1697510 -0.6609320 0.7082350 H 4.4096240 0.2578980 -0.1609470 C -5.2515510 1.2176170 0.3103160 H -5.9828660 2.0086910 0.4559230 C -3.9005170 1.4909240 0.5098040 H -3.5623800 2.4782220 0.8094410 C 1.7803620 -3.5274580 0.9900450 H 2.6018470 -4.1978890 0.7469710 C -5.6720860 -0.0578290 -0.0811390 H -6.7260190 -0.2650990 -0.2399600 C 1.0445950 -3.7323910 2.1577870 H 1.2954690 -4.5590930 2.8162560 C -4.7187180 -1.0612240 -0.2606460 H -5.0292860 -2.0601550 -0.5563480    S10  References [1] X.-W. Zhang, J. Xia, H.-W. Yan, S.-L. Luo, S.-F. Yin, C.-T. Au, W.-Y. Wong, J. Organomet. Chem. 2009, 694, 3019-3026. [2] J. Ramler, I. Krummenacher, C. Lichtenberg, Chem. Eur. J. 2020, 26, 14551-14555. [3] a) D. J. Liptrot, P. M. S. Hill, M. F. Mahon, Angew. Chem. Int. Ed. 2014, 53, 6224-6227; b) R. Schwamm, M. Lein, M. Coles, C. Fitchett, Chem. Commun. 2018, 54, 916-919. [4] M. Tanabe, M. Kamono, K. Tanaka, K. Osakada, Organometallics 2017, 36, 1929-1935. [5] C. Lorenz, U. Schubert, Chem. Ber. 1995, 128, 1267-1269. [6] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, Williams, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, D. J. Fox, Wallingford, CT, 2016. [7] P. C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213-222. [8] a) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283; b) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310; c) T. H. Dunning, P. J. Hay, Methods of Electronic Structure Theory, Vol. 3, Plenum, New York, 1977. [9] A. D. Becke, J. Chem. Phys 1993, 98, 5648-5652. [10] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104. [11] E. Glendening, J. Badenhoop, A. Reed, J. Carpenter, J. Bohmann, C. Morales, P. Karafiloglou, C. Landis, F. Weinhold, Theoretical Chemistry Institute, University of Wisconsin, Madison 2018. [12] T. Yanai, D. P. Tew, N. C. Handy, Chem. Phys. Lett. 2004, 393, 51-57.  

Two Faces of the Bi-O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si-O Bond Formation

https://archiv.ub.uni-marburg.de/es/2022/0015/pdf/ejic_si.pdf

Two Faces of the Bi O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si O Bond Formation

Abstract

Similar works

Full text

Available Versions

Publikations- und Dokumentenserver der Universitätsbibliothek Marburg