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Uranium and Thorium Complexes of the Phosphaethynolate Ion

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Uranium and Thorium Complexes of the Phosphaethynolate Ion Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2015 Supporting Information Uranium and Thorium Complexes of the Phosphaethynolate Ion Clément Camp,a Nicholas Settineri,a Julia Lefèvre,b Andrew R. Jupp,c Jose M. Goicoechea,c Laurent Maron*,b and John Arnold*,a a Heavy Element Chemistry Group, Chemical Sciences Division, Lawrence Berkeley National Laboratory and Department of Chemistry, University of California, Berkeley, California 94720, United States. [email protected] b LPCNO, Université de Toulouse, INSA Toulouse, 135 Avenue de Rangueil, 31077 Toulouse, France. [email protected] c Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. [email protected] Content A. Experimental section.......................................................................................................................2 B. NMR and IR spectroscopic data.......................................................................................................5 C. X-ray crystallography.....................................................................................................................14 D. DFT calculations.............................................................................................................................18 E. References.....................................................................................................................................67 1 A. Experimental section General Considerations. Unless otherwise noted, all reactions were performed either using standard Schlenk line techniques or in an MBraun inert atmosphere glovebox under an atmosphere of purified nitrogen (<1 ppm O2/H2O). Glassware and cannulae were stored in an oven at ∼160 °C for at least 12 h prior to use. Hexanes, THF and toluene were purified by passage through a column of activated alumina, stored over 3 or 4 Å molecular sieves, and degassed prior to use. C6D6 was dried over sodium/benzophenone and then vacuum-transferred to a storage flask and freeze-pump-thaw degassed before being stored over activated [1] [2] [3] [4] molecular sieves in the drybox. UCl4, ThCl4(DME)2, (amid)Li(TMEDA) and Na(OCP)(dioxane)2.9 were prepared using literature procedures. All other reagents were acquired from commercial sources and used as received. NMR spectra were recorded on Bruker AVQ-400, AVB-400, DRX-500, AV-500, and AV-600 spectrometers. Chemical shifts were measured relative to residual solvent peaks, which were assigned relative to an external TMS standard set at 0.00 ppm. 31P chemical shifts were referenced to an external 31 1 13 1 1 standard (Ph3PO for P set at 23 ppm). H and C NMR assignments were routinely confirmed by H− H COSY and 1H−13C HSQC experiments. Infrared (IR) spectra were recorded with a Thermo Scientific Nicolet iS10 series FTIR spectrophotometer as a Nujol mull between KBr plates. The uncorrected melting points were determined using sealed capillaries prepared under nitrogen on an Optmelt SRS. Elemental analyses were performed at the School of Human Sciences, Science Center, London Metropolitan University. The X-ray structural determinations were performed at CHEXRAY, University of California, Berkeley on a Bruker SMART APEX II QUAZAR diffractometer. Solution magnetic moments were obtained by Evan’s Method. Details concerning X-ray diffraction analyses and DFT computational studies are provided in the following sections. Synthetic methods Ph TMS TMS Ph N N 1) THF Cl TMS TMS 2) Toluene TMS TMS UCl + 3 N N N N 4 Li r.t. U 2MeN NMe2 - 3 LiCl - 3 TMEDA Ph N N Ph TMS TMS 1 green crystals, 88% Ph TMS TMS Ph N N 1) THF Cl TMS TMS 2) Toluene TMS TMS N N N N ThCl4(DME)2 + 3 Th Li r.t. 2MeN NMe2 - 3 LiCl - 3 TMEDA Ph N N Ph TMS TMS 2 colorless crystals, 59% UCl(amid)3 (1) This compound was prepared according to a modified published procedure.[5] A 50 mL THF solution of (amid)Li(TMEDA) (3.15 g, 8.13 mmol, 3 equiv.) was added to UCl4 (1.03 g, 2.71 mmol, 1 equiv.) and the reaction mixture was vigorously stirred at room temperature for 15 h affording a green suspension. The THF solvent was then removed in vacuo and the residue was triturated with 2x10 mL toluene and taken to dryness. The green residue was then extracted with 3x30mL toluene and filtered. The resulting green filtrate was concentrated to 30 mL and allowed to crystallize at -40°C in a freezer for 24 h. This produced large bright green crystals that were recovered and dried in vacuo (2.55 g, 88 % yield). The crystal [5] 1 structure for 1 was previously reported by Edelmann and coworkers. H NMR (400 MHz, C6D6, 293 K) δ = 15.3 (br s, 3H, CHAr), 10.9 (br s, 3H, CHAr), 9.3 (br s, 6H, CHAr), 8.8 (t, 3H, CHAr), 1.3 (s, 27H, SiMe3), -3.1 -1 (s, 27H, SiMe3). FT-IR (cm ) 2915 (s), 2851 (s), 1463 (s), 1386 (s), 1245 (s), 1157 (w), 1075 (w), 1000 (w), 973 (s), 920 (w), 841 (s), 784 (s), 759 (s), 704 (s), 477(s). M.p. 317(2)°C, decomp. Anal. calcd for C39H69ClN6Si6U: C, 44.02; H, 6.54; N, 7.90. Found: C, 43.98; H, 6.47; N, 7.93. 2 ThCl(amid)3 (2) This compound was prepared in an analogous fashion to that previously stated for 1. (amid)Li(TMEDA) (5.01 g, 12.9 mmol, 3 equiv.) and ThCl4(DME)2 (2.39 g, 4.3 mmol, 1 equiv.) yielded 2.71 g of 2 (59 % yield). Colorless crystals suitable for X-ray diffraction were grown from a concentrated toluene solution 1 kept at -40 °C for 24 h. H NMR (500 MHz, C6D6, 293 K) δ = 7.5 (br s, 6H, CHAr), 7.0 (m, 9H, CHAr), 0.4 (s, -1 27H, SiMe3), 0.2 (s, 27H, SiMe3). FT-IR (cm ) 2922 (s), 2853 (s), 1463 (s), 1246 (s), 1160 (w), 1025 (w), 1000 (w), 978 (s), 920 (w), 842 (s), 785 (m), 761 (s), 717 (s), 479 (s). M.p. 317(2)°C, decomp. Anal. calcd for C39H69N6Si6ClTh: C, 44.15; H, 6.84; N, 7.92. Found: C, 44.16; H, 6.71; N, 7.85. U(OCP)(amid)3 (3) A 10 mL THF solution of UCl(amid)3 (300 mg, 0.282 mmol, 1 equiv.) and Na(OCP)(dioxane)2.9 (100 mg, 0.296 mmol, 1.05 equiv.) was stirred at room temperature for 24 h. The THF solvent was then removed in vacuo and the residue was extracted with 2 mL toluene and filtered. The green filtrate was allowed to crystallize at -40°C in a freezer for 48 h. This produced green block-shaped crystals that were recovered and dried in vacuo (234 mg, 76 % yield). Single crystals suitable for X-ray diffraction were obtained similarly. 1H NMR (400 MHz, C6D6, 293 K) δ = 13.7 (br s, 3H, CHAr), 10.3 (br s, 3H, CHAr), 8.9 (t, 6H, CHAr), 8.4 (t, 3H, CHAr), 0.5 (s, 27H, 31 13 SiMe3), -2.6 (s, 27H, SiMe3). P NMR (243 MHz, C6D6, 293 K) δ = -285.2 (s, OCP). C NMR (125.8 MHz, C6D6, -1 293 K) δ = 142.7 (CAr), 132.9 (CAr), 4.6 (SiMe3), 1.8 (SiMe3). FT-IR (cm ) 2955 (s), 2925 (s), 2852 (s), 1685 (s, PCO), 1463 (s), 1386 (s), 1247 (s), 1179 (w), 1157 (w), 1000 (w), 974 (s), 931 (w), 920 (w), 838 (s), 783 (s), 761 (s), 704 (s). M.p. 233(2)°C, decomp. μeff = 3.23 μB (C6D6, 293 K, Evans’method). Anal. calcd for C40H69N6OPSi6U: C, 44.18; H, 6.40; N, 7.73. Found: C, 43.83; H, 6.31; N, 7.62. Th(OCP)(amid)3 (4) This compound was prepared in an analogous fashion to that previously stated for 3. ThCl(amid)3 (298 mg, 0.282 mmol, 1 equiv.) and Na(OCP)(dioxane)2.9 (100 mg, 0.296 mmol, 1.05 equiv.) yielded 191 mg of 4 (63%). Colorless crystals suitable for X-ray diffraction were grown from a concentrated toluene 1 solution kept at -40 °C for 24 h. H NMR (400 MHz, C6D6, 293 K) δ = 7.3 (br s, 6H, CHAr), 7.0 (m, 9H, CHAr), 31 13 0.3 (s, 27H, SiMe3), 0.1 (s, 27H, SiMe3). P NMR (243 MHz, C6D6, 293 K) δ = -334.4 (s, OCP). C NMR (125.8 MHz, C6D6, 293 K) δ = 181.7 (NCN), 143.0 (CAr), 128.8 (CAr), 126.8 (CAr), 3.4 (SiMe3), 2.7 (SiMe3). FT- IR (cm-1) 2923 (s), 2853 (s), 1683 (s, PCO), 1385 (s), 1248 (s), 978 (s), 839 (s), 785 (s), 761 (s), 703 (s). M.p. 277(2)°C, decomp. Anal. calcd for C40H69N6OPSi6Th: C, 44.42; H, 6.43; N, 7.77. Found: C, 44.35; H, 6.35; N, 7.69. U(NCO)(amid)3 (5) A 5 mL THF suspension of UCl(amid)3 (195 mg, 0.183 mmol, 1 equiv.) and sodium cyanate (13.7 mg, 0.211 mmol, 1.15 equiv.) was stirred at room temperature for 24 h. The THF solvent was then removed in vacuo and the residue was extracted with 1.5 mL toluene and filtered. The green filtrate was allowed to crystallize at -40°C in a freezer for 48 h. This produced green block-shaped crystals that were recovered and dried in vacuo (123 mg, 63 % yield). Single crystals suitable for X-ray diffraction were obtained similarly. 1H NMR (400 MHz, C6D6, 293 K) δ = 13.2 (br s, 3H, CHAr), 10.1 (br s, 3H, CHAr), 8.8 (t, 6H, CHAr), 8.4 (t, 3H, CHAr), 0.5 (s, 27H, 13 SiMe3), -2.5 (s, 27H, SiMe3). C NMR (125.8 MHz, C6D6, 293 K) δ = 144.0 (CAr), 132.7 (CAr), 3.4 (SiMe3), 1.9 -1 (SiMe3). FT-IR (cm ) 3063 (w), 2922 (s), 2853 (s), 2199 (s, OCN), 1398 (s), 1246 (s), 1157 (w), 1074 (w), 1000 (w), 973 (s), 920 (w), 847 (s), 784 (s), 758 (s), 706 (s).
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