Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Heavier chalcogenone complexes of bismuth(iii)trihalides: Potential catalysts for acylative cleavage of cyclic ethers Katam Srinivas, Paladugu Suresh, Chatla aga Babu, Arruri Sathyanarayana and Ganesan Prabusankar* Department of Chemistry, Indian Institute of Technology Hyderabad, DF Campus, Yeddumailaram, AP, IDIA-502 205. Fax: +91 40 2301 6032; Tel: +91 40 2301 6089; E-mail: prabu@iith.ac.in Ph Me S S Me Bi Williams et al. (1989) S R' R' R' S [1:2] H B S Bi S R' S Ph Bi Shu et al. (2004) [1:3] Ph R' S R' R Bi S R' Supporting Information H X' R' X' B R' X' R S R S S R R Bi X S S R S R X' B X' R' R' X' H R = Me, X' = C, R' = H, X = Tp 2 a R = Me, X' =, R' = Me, X = R = Et, X' =, R' = Me, X = 3 R = Ph, R' = Me, X' =, X = 3 Reglinski et al. (1999) Bailey et al. (2001) Marchio et al. (2003) Marchio et al. (2004) [1:6] R = R' = Et R = Me, R' = ipr R = Me, R' = Pr Battaglia et al. (1983) Williams et al. (2007) [1:2] Me S HB Bi S Me S Me Me S Me S Bi S BH Me nbu nbu Se I nbu Singh et al. (2013) [1:1] I Bi I I nbu Se Bi I I I I Bi nbu I I Bi Se Reglinski et al. (1999) [1:3] I nbu I Se nbu nbu Scheme S1. The structurally characterized monomeric, dimeric and tetrameric bismuth complexes of imazolyl heavier chalcogenone. Page 1 of 27
1325.10 Transmittance [%] 75 80 85 90 95 3050.34 2958.46 2925.29 2865.23 1593.51 1465.47 1407.61 1381.79 1360.32 1257.68 1272.86 1209.02 1060.33 1105.95 937.82 801.27 738.79 752.36 767.00 678.46 636.30 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S1. FT-IR (neat) spectrum of IPr=Te (5) at RT. Figure S2. 1 H MR spectrum of IPr=Te (5) in CD 3 at RT. Page 2 of 27
Figure S3. 13 C MR spectrum of IPr=Te (5) in CD 3 at RT. 802.14 Transmittance [%] 88 90 92 94 96 98 2961.55 2926.47 2867.11 1548.71 1592.21 1327.36 1463.91 1364.43 1209.28 1385.30 1260.17 1102.81 1059.99 1020.30 1041.42 1409.58 1182.20 936.37 754.03 578.20 678.41 626.28 546.33 529.16 513.03 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S4. FT-IR (neat) spectrum of [(IPr=Te)Bi 3 ] (10) at RT. Page 3 of 27
802.02 Transmittance [%] 84 86 88 90 92 94 96 98 100 2960.98 2925.93 2866.44 3050.10 1716.28 1326.51 1462.06 1363.93 1209.28 1546.97 1384.44 1259.52 1148.59 1592.34 1408.92 1104.94 1060.05 1042.03 937.56 1182.90 970.01 753.49 636.13 680.15 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S5. FT-IR (neat) spectrum of [(IPr=Te)BiBr 3 ] (11) at RT. 2921.53 751.22 Transmittance [%] 86 88 90 92 94 96 98 100 2958.01 2853.13 1460.54 1369.90 1419.54 1326.61 1257.51 1212.35 1058.90 936.33 803.68 690.22 664.38 3500 3000 2500 Wavenumber cm-1 2000 1500 1000 Figure S6. FT-IR (neat) spectrum of [(IPr=S)Bi 3 ].CH 3 (6) at RT. C:\Program Files (x86)\pus_65\meas\.2228 GP-KS-L-2-19 SLID 21/12/2013 Page 1/1 Page 4 of 27
Figure S7. 1 H MR spectrum of [(IPr=S)Bi 3 ].CH 3 (6) in CD 3 at RT. Page 5 of 27
Figure S8. 13 C MR spectrum of [(IPr=S)Bi 3 ].CH 3 (6) in CD 3 at RT. 1364.94 752.39 Transmittance [%] 95 96 97 98 99 100 2960.20 2923.17 2865.56 1456.47 1328.77 1259.12 1215.05 1179.87 1119.20 1141.07 1100.60 1042.15 1059.17 935.92 804.80 731.03 689.87 572.33 3500 3000 2500 Wavenumber cm-1 2000 1500 1000 Figure S9. FT-IR (neat) spectrum of [(IPr=S)BiBr 3 ].CH 3 (7) at RT. Figure S10. 1 H MR spectrum of [(IPr=S)BiBr 3 ].CH 3 (7) in CD 3 at RT. Page 6 of 27
Figure S11. 13 C MR spectrum of [(IPr=S)BiBr 3 ].CH 3 (7) in CD 3 at RT. 727.79 Transmittance [%] 20 30 40 50 60 70 80 90 100 3054.24 2927.76 2960.85 2866.85 1592.60 1341.12 1212.44 1468.08 1412.76 1383.03 1260.13 1181.61 904.81 1061.56 1094.66 1012.90 937.25 803.07 648.89 683.39 3500 3000 2500 Wavenumber cm-1 2000 1500 1000 Figure S12. FT-IR (neat) spectrum of [(IPr=Se)Bi 3 ].CH 2 2 (8) at RT. Page 7 of 27
Figure S13. 1 H MR spectrum of [(IPr=Se)Bi 3 ].CH 2 2 (8) in CD 3 at RT. Page 8 of 27
Figure S14. 13 C MR spectrum of [(IPr=Se)Bi 3 ].CH 2 2 (8) in CD 3 at RT. 725.26 903.45 Transmittance [%] 20 30 40 50 60 70 80 90 100 3159.23 2926.59 2964.25 2868.89 2253.75 1551.63 1467.65 1422.98 1350.70 1215.04 1260.01 1180.19 1099.61 1060.23 1041.19 975.27 803.30 649.01 3500 3000 2500 Wavenumber cm-1 2000 1500 1000 Figure S15. FT-IR (neat) spectrum of [(IPr=Se)BiBr 3 ].CH 2 2 (9) at RT. Page 9 of 27
Figure S16. 1 H MR spectrum of [(IPr=Se)BiBr 3 ].CH 2 2 (9) in CD 3 at RT. Page 10 of 27
Figure S17. 13 C MR spectrum of [(IPr=Se)BiBr 3 ].CH 2 2 (9) in CD 3 at RT. 1369.43 Transmittance [%] 75 80 85 90 95 3159.61 3132.94 2914.80 2945.01 2133.34 1990.11 2243.60 2162.86 2092.92 2031.83 1437.14 1554.43 1482.92 1600.99 1651.35 1288.08 1239.14 1167.13 1138.52 854.27 1032.66 980.97 926.34 689.82 608.41 761.49 726.49 623.93 641.07 576.09 552.16 523.67 510.89 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S18. FT-IR (neat) spectrum of [(IMesS)Bi() 2 (μ 2 -)] 2.4CH 3 (12) at RT. Page 11 of 27
Figure S19. 1 H MR spectrum of [(IMesS)Bi() 2 (μ 2 -)] 2.4CH 3 (12) in CD 3 at RT. Page 12 of 27
Figure S20. 13 C MR spectrum of [(IMesS)Bi() 2 (μ 2 -)] 2.4CH 3 (12) in CD 3 at RT. 1367.66 Transmittance [%] 75 80 85 90 95 100 3128.96 3155.15 2915.62 2348.78 2218.89 2165.27 2008.51 2032.92 1940.86 1754.13 1437.93 1553.26 1483.05 1601.59 1410.93 1651.21 1287.05 1236.46 1166.54 1138.54 857.42 897.94 1032.28 980.80 926.62 725.13 685.93 607.18 575.37 514.83 533.26 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S21. FT-IR (neat) spectrum of [(IMesS)Bi(Br) 2 (μ 2 -Br)] 2.2CH 3 (13) at RT. Page 13 of 27
Figure S22. 1 H MR spectrum of [(IMesS)Bi(Br) 2 (μ 2 -Br)] 2.2CH 3 (13) in CD 3 at RT. Figure S23. 13 C MR spectrum of [(IMesS)Bi(Br) 2 (μ 2 -Br)] 2.2CH 3 (13) in CD 3 at RT. Page 14 of 27
Transmittance [%] 86 88 90 92 94 96 98 100 3157.24 3129.59 2913.92 2854.70 2315.24 2229.14 2155.07 1986.72 1937.73 2359.01 2254.29 2174.41 2078.79 2012.56 1963.46 1511.56 1481.72 1444.30 1365.20 1234.71 855.38 689.55 1604.05 1550.69 1291.45 1119.75 1034.37 927.89 738.18 572.80 976.93 596.70 1681.28 1165.24 1080.97 795.01 640.65 550.66 510.27 527.29 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S24. FT-IR (neat) spectrum of [(IMesSe)Bi() 2 (μ 2 -)] 2.4CH 2 2 (14) at RT. Figure S25. 1 H MR spectrum of [(IMesSe)Bi() 2 (μ 2 -)] 2.4CH 2 2 (14) in CD 3 at RT. Page 15 of 27
Figure S26. 13 C MR spectrum of [(IMesSe)Bi() 2 (μ 2 -)] 2.4CH 2 2 (14) in CD 3 at RT. Transmittance [%] 90 92 94 96 98 100 2943.29 2912.51 2851.71 2167.12 1954.96 1995.72 1369.56 858.07 1561.45 1510.31 1482.53 1441.45 1411.10 1231.59 1033.08 1293.40 1122.46 927.65 1603.54 1164.99 1083.74 976.48 822.08 721.94 679.65 572.80 644.71 593.02 521.98 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S27. FT-IR (neat) spectrum of [(IMesSe)Bi(Br) 2 (μ 2 -Br)] 2 (15) at RT. Page 16 of 27
Figure S28. 1 H MR spectrum of [(IMesSe)Bi(Br) 2 (μ 2 -Br)] 2 (15) in CD 3 at RT. Page 17 of 27
Figure S29. 13 C MR spectrum of [(IMesSe)Bi(Br) 2 (μ 2 -Br)] 2 (15) in CD 3 at RT. Transmittance [%] 93 94 95 96 97 98 99 100 1603.74 1542.84 1481.71 1441.78 1404.59 1377.86 1320.14 1273.69 1229.72 1091.67 1031.56 1165.60 1107.68 854.02 927.86 733.30 678.27 692.70 572.55 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S30. FT-IR (neat) spectrum of [(IMesTe)Bi() 2 (μ 2 -)] 2 (16) at RT. Transmittance [%] 92 94 96 98 100 1481.95 1442.26 1378.36 1605.74 1546.52 1321.96 1678.55 852.20 1230.63 1094.79 1032.74 928.99 1163.98 1111.53 975.37 733.57 691.73 674.15 571.03 591.48 638.57 3500 3000 2500 2000 Wavenumber cm-1 1500 1000 500 Figure S31. FT-IR (neat) spectrum of [(IMesTe)Bi(Br) 2 (μ 2 -Br)] 2 (17) at RT. D:\DATA\FTIR DATA\Dr.G.PRABUSAKAR\K.SRIIVAS\IMes=Te-BiBr3.0 IMes=Te-BiBr3 solid 25/05/2014 Page 1/1 Page 18 of 27
Figure S32. The solution state UV-vis spectra of 3-5 in DCM at 25 o C (3.8 X 10-2 M). Figure S33. The solid state UV-vis spectra of 3-5. Page 19 of 27
Figure S34. The solution state UV-vis spectra of 3a-5a in DCM at 25 o C (3.8 X 10-2 M). Figure S35. The solid state UV-vis spectra of 3a-5a. Page 20 of 27
Table S1a. Structural parameters of compounds 3, 5-9. 3 5 6 7 8 9 Empirical formula C 6.75 H 9 0.5 S 0.25 C 6.75 H 9 0.5 Te 0.25 C 7 H 9.25 0.5 S 0.25 1.5 Bi 0.25 C 14 H 18.5 S 0.5 Br 1.5 Bi 0.5 1.5 C 7 H 9.5 0.5 1.25 Bi 0.25Se 0.25 C 28 H 38 BiBr 3 2 2Se Formula weight 420.67 516.20 855.38 988.73 867.83 1001.18 Temperature (K) 150 150 150 156 150 150 Crystal system Monoclinic Monoclinic Monoclinic Triclinic Monoclinic Monoclinic Space group P2 1 /n P2 1 /n P2 1 /c Pī P2 1 /c P2 1 /c a/å 19.2174(14) 19.1643(5) 9.6999(3) 10.0168(4) 10.75451(16) 10.7722(2) b/å 6.8155(4) 7.15496(17) 14.6885(5) 12.5839(6) 16.0772(2) 16.3835(3) c/å 20.0755(17) 20.1107(8) 23.7580(7) 15.6771(7) 19.7995(4) 20.0651(4) α/ 90 90 90 73.883(4) 90 90 β/ 101.338(8) 106.852(4) 93.507(3) 76.522(4) 104.6833(16) 103.228(2) γ/ 90 90 90 74.563(4) 90 90 Volume (Å 3 ) 2578.1(3) 2639.17(16) 3378.65(18) 1802.72(15) 3311.58(9) 3447.26(12) Z 4 4 4 2 4 4 ρ calc /mg mm -3 1.0837 1.2991 1.6815 1.8214 1.7405 1.9289 Absorption coefficient (µ/mm -1 ) 1.205 8.989 15.342 16.228 15.567 16.890 F(000) 915.5 1058.3 1678.5 941.0 1680.5 1884.0 Reflections collected 9769 10829 13786 12304 15584 14315 R int 0.0313 0.0333 0.0566 0.0507 0.0364 0.0399 GF on F 2 1.064 1.040 1.023 1.029 1.041 1.033 R 1 (I>2ϭ(I)) 0.0626 0.0354 0.0727 0.0593 0.0384 0.0550 wr 2 (I>2ϭ(I)) 0.178639 0.095047 0.242118 0.163590 0.106819 0.156333 R 1 values (all data) 0.0832 0.0444 0.0828 0.0605 0.0417 0.0593 R 2 values (all data) 0.1786 0.0950 0.2421 0.1636 0.1068 0.1563 Page 21 of 27
Table S1b. Structural parameters of compounds 4a and 12-15. 4a 12 13 14 15 Empirical formula C 21 H 24 2 Se C 46 H 52 Bi 2 18 4 S 2 C 46 H 52 Bi 2 Br 6 12 4S 2 C 23H 28Bi 7 2 Se C 42H 48 4 Se 2 Bi 2 Br 6 Formula weight 383.40 1781.19 2047.90 1737.20 1664.18 Temperature (K) 150 150 150 150 150 Crystal system rthorhombic Monoclinic Triclinic Monoclinic Monoclinic Space group Pbcn P2 1 /n Pī P2 1 /c P2 1 /c a/å 16.0321(9) 12.2653(8) 9.9610(5) 15.9721(6) 9.5278(2) b/å 7.3653(3) 17.1990(9) 13.3493(6) 10.8271(4) 16.1998(4) c/å 16.0280(5) 15.5570(7) 14.3207(7) 18.3916(6) 16.2869(4) α/ 90 90 111.257(5) 90 90.00 β/ 90 99.117(5) 103.339(4) 97.510(3) 98.199(2) γ/ 90 90 97.547(4) 90 90.00 Volume (Å 3 ) 1892.61(14) 3240.3(3) 1677.59(16) 3153.19(19) 2488.15(10) Z 4 2 1 2 2 ρ calc /mg mm -3 1.3455 1.8255 2.0971 1.8296 2.221 Absorption coefficient (µ/mm -1 ) 2.695 18.252 19.615 17.875 21.293 F(000) 790.6 1722.9 963.2 1659.3 1544.0 Reflections collected 3592 12843 11831 14171 10803 R int 0.0281 0.0569 0.0684 0.0374 0.0392 GF on F 2 1.210 1.046 1.050 1.041 1.048 R 1 (I>2ϭ(I)) 0.0426 0.1190 0.0604 0.0531 0.0358 wr 2 (I>2ϭ(I)) 0.321768 0.166247 0.161189 0.0951 R 1 values (all data) 0.0529 0.1368 0.0614 0.0635 0.0406 R 2 values (all data) 0.1721 0.3218 0.1662 0.1612 0.1005 Page 22 of 27
Table S2. Selected bond lengths and angles of compounds 6-9. 6 7 8 9 Bond lengths [Å] Bi(1) E(1) 2.929(2) 2.940(18) 2.971(5) 2.980(8) Bi(1) X(1) 2.578(3) 2.615(8) 2.473(12) 2.620(9) Bi(1) X(2) 2.452(3) 2.731(9) 2.486(13) 2.760(9) Bi(1) X(3) 2.479(2) 2.610(8) 2.594(13) 2.630(10) C(1) E(1) 1.696(10) 1.694(7) 1.861(5) 1.861(8) Bond angles [ o ] (1) C(1) (2) 106.1(8) 105.9(6) 106.1(4) 105.9(6) (1) C(1) E(1) 130.1(7) 125.5(5) 125.3(3) 129.2(5) (2) C(1) E(1) 123.7(7) 128.7(5) 108.5(3) 124.8(5) C(1) E(1) Bi(1) 108.8(3) 114.1(2) 110.94(13) 111.5(2) X(1) Bi(1) X(2) 93.08(9) 93.28(3) 90.93(5) 91.21(3) X(1) Bi(1) X(3) 90.27(10) 94.71(3) 89.40(5) 92.86(3) X(2) Bi(1) X(3) 94.70(9) 93.76(3) 94.48(5) 94.19(3) X(1) Bi(1) E(1) 70.47(9) 80.75(4) 75.33(3) 76.53(3) X(2) Bi(1) E(1) 84.60(8) 172.70(5) 103.09(3) 160.92(3) X(3) Bi(1) E(1) 80.73(8) 90.94(5) 156.73(4) 100.88(3) Page 23 of 27
Table S3. Selected bond lengths and angles of compounds 4a, 12-15. 4a 12 13 14 15 Bond lengths [Å] Bi(1) E(1) 2.874(5) 2.778(2) 2.8931(10) 2.9251(7) Bi(1) X(1) 2.509(4) 2.6827(9) 2.523(2) 2.7084(8) Bi(1) X(2 1 ) 2.693(5) 2.9146(9) 2.763(2) 3.0744(7) Bi(1) X(3) 2.482(5) 2.6330(9) 2.485(2) 2.6152(7) C(1) E(1) 1.827(6) 1.683(19) 1.703(9) 1.870(9) 1.866(6) Bond angles [ o ] (1) C(1) (1) 104.8(5) 104.1(15) 109.9(7) 106.3(7) 105.9(5) (1) C(1) E(1) 127.6(3) 131.3(12) 123.1(6) 129.0(7) 129.6(4) (2) C(1) E(1) 124.6(14) 130.2(6) 124.7(7) 124.5(4) X(1) Bi(1) X(2 1 ) 88.08(15) 90.64(3) 87.88(8) 169.94(2) X(1) Bi(1) E(1) 94.60(15) 93.55(5) 91.26(6) 97.88(2) X(3) Bi(1) X(1) 90.73(15) 90.08(3) 90.45(8) 88.10(3) X(3) Bi(1) X(2 1 ) 90.66(19) 93.52(3) 87.82(7) 87.30(2) X(3) Bi(1) E(1) 77.37(15) 81.18(5) 75.14(5) 79.27(2) E(1) Bi(1) X(2 1 ) 167.75(17) 173.24(5) 162.94(5) 90.05(2) C(1) E(1) Bi(1) 112.6(6) 110.8(3) 109.8(3) 108.54(19) Page 24 of 27
Table S4. Preparation of 4-chloropentylacetate. MeC 2.5 mol% catalyst DCM, RT, 2 h 78-100% Entry Catalyst Starting Material Conversion (%) a Yield (%) b 1 IPrS-BiBr 3 (7) 88 80 2 IPrSe-Bi 3 (8) 96 90 3 IPrSe-BiBr 3 (9) 85 78 4 IPrTe-Bi 3 (10) 80 76 5 IPrTe-BiBr 3 (11) 78 75 6 IMesS-Bi 3 (12) 94 90 7 IMesS-BiBr 3 (13) 88 80 8 IMesSe-Bi 3 (14) 92 88 9 IMesSe-BiBr 3 (15) 86 82 10 IMesTe-Bi 3 (16) 84 80 11 IMesTe-BiBr 3 (17) 79 70 12 IPrS & Bi 3 95 90 13 Bi 3 92 88 14 BiBr 3 90 85 15 Without catalyst 0 0 a The starting materials conversion was calculated after 2h. b % Yields were calculated based on the weight of products and the starting material conversion. Page 25 of 27
Table S5. Bismuth(III) mediated -acylative cleavage of different cyclic ethers. Entry Starting Materials Product Time (h) a Starting Material Conversion (%) Yiel d (%) c 1 Ph 48 94 88 2 Me Me Me Me 2 100 99 3 Me Ph Me 4 100 99 4 Me Me 48 30 28 5 48 20 18 Ph 6 Me Me 48 15 b 12 7 Ph 48 10 b 8 a = The obtimized time is 2h, however the reaction time was increased since the reaction was too slow. b =o further conversion after 48 h; c = % Yields were calculated based on the weight of the product with respect to the starting material. Page 26 of 27
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