Organometallic clusters as precursors of metallic nanoparticles 6

Appendix Chapter 2.1 ToF-SIM No Figure caption 2.1.1 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a dichloromethane solution of Os3(CO)10(μ-H)(μ-OH), 2.1.2 ToF-SIMS spectrum (positive ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)2, 22 2.1.13 ToF-SIMS spectrum (positive mode) of a ZnO substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)2, 22 2.1.12 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a 2.1.11 ToF-SIMS spectrum (positive ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a 2.1.10 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a dichloromethane solution of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a 2.1.9 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a 2.1.8 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)2OH], 9a 2.1.7 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 2.1.6 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 2.1.5 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 2.1.4 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)(μ-OH), 2.1.3 Page ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)2SH], 23a 2.1.14 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a dichloromethane solution of Os3(CO)10(μ-H)[μ-S(CH2)2SH], 23a 2.2 NMR No Figure caption Page 2.2.1 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3SH], 4a in CDCl3 2.2.2 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a in CDCl3 2.2.3 NMR spectrum of Os3(CO)10(μ-H)[μ-SCH2(1,4-C6H4)CH2SH], 6a in CDCl3 10 2.2.4 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a in CDCl3 11 2.2.5 NMR spectrum of Os3(CO)10(μ-H)(μ-SC=NNCSS-μ3, η2)Os3(CO)9(μ-H), in CDCl3 12 2.2.6 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2OH], 9a in CDCl3 13 2.2.7 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a in CDCl3 14 2.2.8 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,2-C6H4)OH], 11a in CDCl3 15 2.2.9 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a in CDCl3 16 2.2.10 NMR spectrum of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a in CDCl3 17 2.2.11 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a in CDCl3 18 2.2.12 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)2COOH, 14a(Ru) in CDCl3 19 2.2.13 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a in CDCl3 20 2.2.14 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a(Ru) in CDCl3 21 2.2.15 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a in CDCl3 22 2.2.16 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a(Ru) in CDCl3 23 2.2.17 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a in CDCl3 24 2.2.18 NMR spectrum of Ru3(CO)10(μ-H)2[μ-S(CH2)10COOH], 17a(Ru) in CDCl3 25 2.2.19 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a in CDCl3 26 2.2.20 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a(Ru) in CDCl3 27 2.2.21 NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)11COOH], 19a in CDCl3 28 2.2.22 NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)4OH], 20a in CDCl3 29 2.2.23 NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)12OH], 21a in CDCl3 2.2.24 30 NMR spectrum of [Os3(CO)10(μ-H)(μ-O)]{Si7O10[(CH2)5CH(CH3)2]7}, 28 in CDCl3 31 2.2.25 NMR spectrum of [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 in CDCl3 32 2.2.26 NMR spectrum of [Os3(CO)10(μ-H)][μ-O(CH2)3Si8O12(i-butyl)7], 30 in CDCl3 2.2.27 H NMR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in CDCl3 2.2.28 33 34 31 P NMR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in CDCl3 35 NMR spectrum of [Os3(CO)10][P(C6H5)2(CH2)2Si8O12(C5H5)7]2, 32b in CDCl3 36 No Figure caption Page 2.3.1 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3SH], 4a in toluene 37 2.3.2 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a in toluene 37 2.3.3 IR spectrum of Os3(CO)10(μ-H)[μ-SCH2(1,4-C6H4)CH2SH], 6a in hexane 38 2.3.4 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a in toluene 38 2.3.5 IR spectrum of Os3(CO)10(μ-H)(μ-SC=NNCSS-μ3, η2)Os3(CO)9(μ-H), 2.2.29 2.3 IR hexane 39 2.3.6 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2OH], 9a in toluene 39 2.3.7 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a in toluene 40 2.3.8 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,2-C6H4)OH], 11a in hexane 40 2.3.9 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a in toluene 41 2.3.10 IR spectrum of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a in hexane 41 2.3.11 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a in toluene 42 2.3.12 IR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a(Ru) in DCM 42 2.3.13 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a in hexane 43 2.3.14 IR spectrum of Ru3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a(Ru) in hexane 43 2.3.15 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a in hexane 44 2.3.16 IR spectrum of Ru3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a(Ru) in DCM 44 2.3.17 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a in hexane 45 2.3.18 IR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a(Ru) in hexane 45 2.3.19 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a in hexane 46 2.3.20 IR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a(Ru) in hexane 46 2.3.21 IR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)11COOH], 19a in hexane 47 2.3.22 IR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)4OH], 20a in hexane 47 2.3.23 IR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)12OH], 21a in hexane 48 2.3.24 IR spectrum of [Os3(CO)10(μ-H)(μ-O)]{Si7O10[(CH2)5CH(CH3)2]7}, 28 in hexane 48 2.3.25 IR spectrum of [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 in hexane 49 2.3.26 IR spectrum of [Os3(CO)10(μ-H)][μ-O(CH2)3Si8O12(i-butyl)7], 30 in hexane 49 2.3.27 IR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in hexane 50 2.3.28 IR spectrum of [Os3(CO)10][P(C6H5)2(CH2)2Si8O12(C5H5)7]2, 32b in hexane 50 No Figure caption Page 2.4.1 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)3SH], 4a 51 2.4.2 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 51 2.4.3 Mass spectrum positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(1,3-C6H4)S], 5b 52 2.4.4 Mass spectrum (negative ion mode) of 2.4 MS Os3(CO)10(μ-H)[μ-SCH2(1,4-C6H4)CH2SH], 6a 52 2.4.5 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 53 2.4.6 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(CH2)8S], 7b 53 2.4.7 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a 54 2.4.8 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(1,2-C6H4)CH2OH], 11a 2.4.9 54 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a 55 2.4.10 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-O(CH2)11SH], 12a’ 55 2.4.11 Mass spectrum positive ion mode) of [Os3(CO)10(μ-H)]2[μ-O(CH2)11S], 12b 56 2.4.12 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a 56 2.4.13 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(1, 57 3-C6H4)COO], 15b 2.4.14 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 57 17a 2.4.15 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(CH2)10COO], 58 17b 2.4.16 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)15COOH], 58 18a 2.4.17 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(CH2)15COO], 59 18b 2.4.18 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-OOC(CH2)10OH], 19a 59 2.4.19 Mass spectrum (positive ion mode) of[Os3(CO)10(μ-H) [μ-O(CH2)4OH], 20a 60 2.4.20 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-O(CH2)12OH], 21a 60 2.4.21 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-O(CH2)12O], 21b 61 2.4.22 Mass spectrum (positive ion mode) of Ru3(CO)10(μ-H)[μ-S(1, 3-C6H4)COOH], 14a(Ru) 2.4.23 Mass spectrum (positive ion mode) of Ru3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a(Ru) 2.4.24 61 62 Mass spectrum (negative ion mode) of Ru3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a(Ru) 62 2.5 Crystal parameter No Crystal Page 2.5.1 Crystal parameter for 5a 63 2.5.2 Crystal parameter for 5b 68 2.5.3 Crystal parameter for 74 2.5.4 Crystal parameter for 9a 82 2.5.5 Crystal parameter for 13a 90 2.5.6 Crystal parameter for 14a 95 2.5.7 Crystal parameter for 15a 113 2.5.8 Crystal parameter for 15b 118 Chapter 3.1 ToF-SIMS No Figure caption 3.1.1 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with Os3(CO)10(μ-H)(μ-OH), 3.1.2 128 ToF-SIMS spectrum (negative ion mode) of Au substrate modified with Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 3.1.8 128 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 3.1.7 127 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 3.1.6 127 ToF-SIMS spectrum (positive ion mode) of Au substrate modified with Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 3.1.5 126 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 3.1.4 126 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 3.1.3 Page ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with 129 Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 3.1.9 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a 3.1.10 134 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with Os3(CO)10(μ-H)[μ-S(CH2)2SH], 23a 3.1.20 134 ToF-SIMS spectrum (positive ion mode) of Ag substrate modified with Os3(CO)10(μ-H)2, 22 3.1.19 133 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with Os3(CO)10(μ-H)2, 22 3.1.18 133 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with Os3(CO)10(μ-H)[μ-O(CH2)4OH], 20a 3.1.17 132 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with Os3(CO)10[μ-O(CH2)4OH], 20a 3.1.16 132 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a 3.1.15 131 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a 3.1.14 131 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with Os3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a 3.1.13 130 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with Os3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a 3.1.12 130 ToF-SIMS spectrum (positive ion mode) of Ag NPs modified with Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a 3.1.11 129 135 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with Os3(CO)10(μ-H)(μ-SCOPh), 33 135 3.2 UV No Figure caption 3.2.1 Absorbance spectra as 5a was titrated against Au NPs in ethanol (Each time, 0.0002 mol 5a was titrated to x 10-5 M Au NPs in 20 ml ethanol) 3.2.2 Page 136 Absorbance spectra as 7a was titrated against Au NPs in ethanol (Each time, 0.0002 mol 7a was titrated to x 10-5 M Au NPs in 20 ml ethanol) 136 No Figure caption Page 3.3.1 TEM image of 5a-modified Au NPs 137 3.3.2 TEM image of 7a-modified Au NPs 137 3.3.3 TEM image of 15a-modified Ag NPs 138 3.3.4 TEM image of 17a-modified Ag NPs 138 3.3.5 TEM image of 23a-modified Au NPs 139 3.3.6 Au NPs in ethanol prepared by laser ablation 139 No Figure caption Page 3.4.1 EDX for 5a-modifed Ag NPs 140 3.4.2 EDX for 5a-modifed Au NPs 140 3.4.3 EDX for 7a-modifed Ag NPs 140 3.4.4 EDX for 7a-modifed Au NPs 141 3.4.5 EDX for 12a-modifed Ag NPs 141 3.4.6 EDX for 14a-modifed Ag NPs 141 3.4.7 EDX for 15a-modifed Ag NPs 142 3.4.8 EDX for 17a-modifed Ag NPs 142 3.4.9 EDX for 20a-modifed Ag NPs 142 3.4.10 EDX for 22-modifed Ag NPs 143 3.4.11 EDX for 22-modifed Au NPs 143 3.3 TEM 3.4 EDX 3.4.12 EDX for 23a-modifed Au NPs 143 3.4.13 EDX for 23a-modifed Ag NPs 144 3.4.14 EDX for 24-modifed Ag NPs 144 3.5 FTIR Table 3.5.1 Observed IR Bands for osmium cluster modified Ag / Au substrate / NPs 145 3.6 NMR No Figure caption Page 3.6.1 NMR spectrum of (6-bromohexyloxy)methyl-15-crown-5, 35 in CDCl3 146 3.6.2 NMR spectrum of (6-mercaptohexyloxy) methyl-15-crown-5, 36 in CDCl3 146 3.6.3 NMR spectrum of Os3 (CO)10(μ-H) [(6-mercaptohexyloxy)methyl-15-crown-5, 37 in CDCl3 147 Chapter 4.1 TGA-DTA No Figure caption Page 4.1.1 TGA-DTA data of Os3(CO)10(μ-H)(μ-OH), 148 4.1.2 TGA-DTA data of Ru3(CO)12, 3(Ru) 148 4.1.3 TGA-DTA data of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 149 4.1.4 TGA-DTA data of Os3(CO)10(μ-H)2, 22 149 4.1.5 TGA-DTA data of [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 150 4.1.6 TGA-DTA data of Os3(CO)11(NCCH3), 31 150 4.1.7 TGA-DTA data of Os2(CO)6I2, 40 151 4.1.8 TGA-DTA data of [Os(CO)2I2]n, 41 151 4.1.9 TGA-DTA data of [Ru(CO)4]n, 42 152 4.1.10 TGA-DTA data of Os3(CO)11(PPh3), 43 152 4.1.11 TGA-DTA data of Os3(CO)11(SbPh3), 44 153 4.1.12 TGA-DTA data of Os3(CO)10(AsPh3)2, 45 153 4.1.13 TGA-DTA data of Os3(CO)10(SbPh3)2, 46 154 4.1.14 TGA-DTA data of RuOs3(CO)13(μ-H)2, 48 154 4.1.15 TGA-DTA data of Os3(CO)10(μ-AuPPh3)2, 50 155 4.1.16 TGA-DTA data of Os3(CO)12Br2, 52 155 No Figure caption Page 4.2.1 X-ray diffraction patterns of the Os NPs from (a) 40, (b) needle shaped 1, (c) 4.2 XRD 41 4.2.2 156 X-ray diffraction patterns of the Os NPs from (a) 31, (b) 43, (c) 44, (d 45, (e) 46 and (f) 47 156 XRD patterns of supported osmium, ruthenium and mixed metals catalysts 156 No Figure caption Page 4.3.1 UV-vis adsorption spectra of Os NPs (in DOE) from different precursors and 4.2.3 4.3 UV precursors (a) Os NPs from Os(CO)4I2; (b) Os NPs from Os2(CO)6I2; (c) Os NPs from Os3(CO)12; (d) Os(CO)4I2; (e) Os3(CO)12 157 UV-vis adsorption spectra of Ru NPs (in DOE) from Ru3(CO)12 157 No Figure caption Page 4.4.1 IR spectra of the thermolysis of Ru3(CO)12, 3(Ru) in DOE: (a) pure 3(Ru), (b) 4.3.2 4.4 IR immediately after injection of 3(Ru) 4.4.2 Reaction spectra of thermolysis of Os(CO)4I2 in DOE: (a) Os(CO)4I2 in DOE, (b) immediately after injection of Os(CO)4I2, (c) after minutes 4.4.3 158 158 Reaction spectra of thermolysis of Os(CO)4I2 in DOE: (a) Os(CO)4I2 in DOE, (b) immediately after injection of Os(CO)4I2, (c) after minutes 159 Appendix 4.4 IR Figure 4.4.1 IR spectra of the thermolysis of Ru3(CO)12, 3(Ru) in DOE: (a) pure 3(Ru), (b) immediately after injection of 3(Ru) 2200 2150 2100 2050 2000 1950 1900 1850 1800 Figure 4.4.2 Reaction spectra of thermolysis of Os(CO)4I2 in DOE: (a) Os(CO)4I2 in DOE, (b) immediately after injection of Os(CO)4I2, (c) after minutes a b c 2200 2180 2160 2140 2120 2100 2080 2060 2040 2020 2000 -1 Wavelength (cm ) 158 Appendix Figure 4.4.3 Reaction spectra of thermolysis of 40 in DOE: (a) 40, (b) after minutes, (c) after 10 minutes, (d) after 20 minutes Transmittance a b c d 2200 2150 2100 2050 2000 1950 1900 Wavelength (nm) Figure 4.4.4 Reaction crude IR spectrum of thermolysis of Os3(CO)12, 3(Os) in DOE: (a) 3(Os), (b) after minutes, (c) after 10 minutes, (d) after 30minutes a b c d 2140 2120 2100 2080 2060 2040 2020 2000 1980 1960 Wavelength (nm) 159 Appendix Figure 4.4.5 IR spectrum of Os3(μ-H)(CO)10[(6-mercaptohexyloxy)methyl-15-crown-5], 37 in DCM 105 %T 100 95 90 85 80 2100 2080 2060 os3crown-c6sh in dcm 2040 2020 2000 1990 1/cm 160 Appendix 4.5 TEM Figure 4.5.1 TEM image of NPs from Os3(CO)12, 3(Os) nm Figure 4.5.2 TEM image of a TiO2 supported catalyst from Os3(CO)12, 3(Os) 161 Appendix Figure 4.5.3 TEM images of NPs from Ru3(CO)12, 3(Ru) Figure 4.5.4 TEM image of a silica supported catalyst from Ru3(CO)12, 3(Ru) Figure 4.5.5 TEM image of NPs from Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a 162 Appendix Figure 4.5.6 TEM image of NPs from Os3(CO)10(μ-H)2, 22 Figure 4.5.7 TEM image of NPs from Os3(CO)11(NCCH3), 31 163 Appendix Figure 4.5.8 TEM image of NPs from Os4(CO)12(μ-H)4, 38 Figure 4.5.9 TEM image of NPs from Os6(CO)18, 39 164 Appendix Figure 4.5.10 TEM images of NPs from Os2(CO)6I2, 40 2.08 2.08 nm Figure 4.5.11 TEM images of NPs from Os(CO)4I2, 41 2.18 2.19 2.03 nm Figure 4.5.12 TEM images of NPs from [Ru(CO)4]n, 42 165 Appendix Figure 4.5.13 TEM image of a TiO2 supported catalyst from [Ru(CO)4]n, 42 Figure 4.5.14 TEM image of NPs from Os3(CO)11(SbPh3), 44 166 Appendix Figure 4.5.15 TEM image of NPs from Os3(CO)10(AsPh3)2, 45 Figure 4.5.16 TEM image of NPs from Os3(CO)10(SbPh3)2, 46 167 Appendix Figure 4.5.17 TEM image of a silica supported catalyst from Os3(CO)10(μ-AuPPh3)2, 50 Figure 4.5.18 TEM image of a silica supported catalyst fromRuCl3, 51 168 Appendix 4.6 EDX Figure 4.6.1 EDX spectrum of the Os film from [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 deposited on silica wafer at 400 oC Figure 4.6.2 EDX spectrum of the Os film from [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 deposited on silica wafer at 500 oC 169 Appendix Figure 4.6.3 EDX spectrum of the Os film from Os2(CO)6I2, 41 deposited on silica wafer at 400 o C Figure 4.6.4 EDX spectrum of the Os film from Os2(CO)6I2, 41 deposited on silica wafer at 500 o C 170 Appendix Figure 4.6.5 EDX for Os3(CO)11(PPh3), 43-derived NPs Figure 4.6.6 EDX for Os3(CO)10(AsPh3), 45-derived NPs 171 Appendix Figure 4.6.7 EDX spectrum of the Os film from Os3(CO)12Br2, 52 deposited on silica wafer at 400 o C Figure 4.6.8 EDX spectrum of the Os film from Os3(CO)12Br2, 52 deposited on silica wafer at 500 o C 172 ... : PROCNO -17.4047 2.37 36 1.9037 1.8817 1.8597 1.8 362 1.8142 1.5538 1.2589 0.9792 0. 969 6 0.9572 0.94 76 0 .62 65 0 .61 96 0 .60 31 0.5 962 0. 069 9 7 .60 64 7. 260 6 6. 91 06 NAME ma01 06 : *** Acquisition Parameters... -17.40 76 2.38 16 2.3 568 2.3294 1 .65 88 1 .63 68 1 .60 94 1.58 46 1.5599 1.5187 1.2 768 3 .65 94 3 .63 75 3 .61 55 7.2595 10.7578 10 .65 06 10.4500 10.30 16 *** Current Data Parameters *** NAME : AP29 163 0 EXPNO... 1.3840 1.3758 1.3483 1.3208 1.31 26 1.2 961 1 .66 16 1 .63 96 1 .63 13 1 .60 66 1.5819 1. 562 6 1.5571 1.5352 2.38 16 2.3 568 2.3321 2.5547 2.5300 2.5052 2.4805 INSTRUM : AM 64 2500.00 Hz PULPROG : SFO1 : 300.1325000