Organometallic clusters as precursors of metallic nanoparticles 6

Chapter 2 2.1 ToF-SIM 2.1.1 ToF-SIMS spectrum negative ion mode of silicon wafer soaked in a 2.1.3 ToF-SIMS spectrum negative ion mode of a ZnO substrate soaked in a 2.1.4 ToF-SIMS spec

Chapter 2

2.1 ToF-SIM

2.1.1 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

2.1.3 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a

2.1.4 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

2.1.6 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

2.1.8 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

2.1.10 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a

2.1.11 ToF-SIMS spectrum (positive mode) of a ZnO substrate soaked in a

2.1.14 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

2.2.24 NMR spectrum of [Os3(CO)10(μ-H)(μ-O)]{Si7O10[(CH2)5CH(CH3)2]7}, 28 in

2.3.16 IR spectrum of Ru3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a(Ru) in DCM 44

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

2.4 MS

2.4.11 Mass spectrum positive ion mode) of [Os3(CO)10(μ-H)]2[μ-O(CH2)11S], 12b 56

No Crystal Page

Chapter 3

3.1 ToF-SIMS

3.1.9 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with

3.1.10 ToF-SIMS spectrum (positive ion mode) of Ag NPs modified with

3.1.11 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with

3.1.12 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with

3.1.13 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with

3.1.14 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with

3.1.15 ToF-SIMS spectrum (negative ion mode) of Ag NPs modified with

3.1.16 ToF-SIMS spectrum (negative ion mode) of Ag substrate modified with

3.1.17 ToF-SIMS spectrum (negative ion mode) of Au NPs modified with

No Figure caption Page

3.3 TEM

3.4 EDX

3.4.13 EDX for 23a-modifed Ag NPs 144

4.1.13 TGA-DTA data of Os3(CO)10(SbPh3)2, 46 154

4.2 XRD

4.4 IR

3(Os), (b) after 2 minutes, (c) after 10 minutes, (d) after 30 minutes 159

4.5 TEM

4.6 EDX

[Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 deposited on silica wafer at

[Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 deposited on silica wafer at

Appendix

Chapter 2

2.1 ToF-SIMS

Figure 2.1.1 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

Figure 2.1.3 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a

Figure 2.1.4 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

Figure 2.1.5 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a

Figure 2.1.6 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

Figure 2.1.7 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a

857 875

Os3(CO)6SH

Os3(CO)7SH

Os3(CO)8SH

Figure 2.1.8 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

Figure 2.1.9 ToF-SIMS spectrum (positive ion mode) of an In2O3 substrate soaked in a

729

Os3(CO)9SH Os3(CO)5SH

Os3(CO)6SH

Os3(CO)7SH

Os3(CO)8SH

Figure 2.1.10 ToF-SIMS spectrum (negative ion mode) of a ZnO substrate soaked in a

800 0

Figure 2.1.11 ToF-SIMS spectrum (positive mode) of a ZnO substrate soaked in a

757 701

Figure 2.1.13 ToF-SIMS spectrum (negative ion mode) of an In2O3 substrate soaked in a

936 906 857

829 800

772

743

715

Os3(CO)8SH

Figure 2.1.14 ToF-SIMS spectrum (negative ion mode) of silicon wafer soaked in a

(ppm)

Figure 2.2.2 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)SH], 5a in CDCl3

7.3474 7.3227 7.2870 7.2402 7.1990 7.1495 7.1083 7.0479 6.9709

(ppm)

6.90 7.00 7.10 7.20 7.30 7.40

Figure 2.2.3 NMR spectrum of Os3(CO)10(μ-H)[μ-SCH2(1,4-C6H4)CH2SH], 6a in CDCl3

7.1592 3.4110

3.7584 3.7144 3.6182

(ppm) 3.6 3.8 0.2639 0.9555 1.1052 0.4171

1.8045 1.7715 1.7220 1.5571

(ppm) 1.60 1.70 1.80

(ppm) -17.4

Os3(CO)10HOH +HSCH2PHCH2SH band4 retlc band1

Figure 2.2.4 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a in CDCl3

*** Acquisition Parameters ***

INSTRUM : AM

NS : 64 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz Os3(CO)10HOH +HS(CH2)8SH rtlc band1

(ppm)

Figure 2.2.5 NMR spectrum of Os3(CO)10(μ-H)(μ-SC=NNCSS-μ3, η2)Os3(CO)9(μ-H), 8 in CDCl3

6

7

*** Current Data Parameters ***

NAME : MA0315B3 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

NS : 16 O2 : 50000.00 Hz SFO1 : 300.1309050 MHz

SW : 45.0250 ppm SW_h : 13513.514 Hz

Figure 2.2.6 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2OH], 9a in CDCl3

2 2.

(ppm) 2.6 2.8

(ppm)

Figure 2.2.7 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a in CDCl3

*** Acquisition Parameters ***

INSTRUM : amx500

NS : 16 O1 : 3000.00 Hz PULPROG : zg SFO1 : 500.1330000 MHz

SR : 5421.06 Hz s3oh purified

1.3572 1.3369 1.2555

(ppm) 1.2

Figure 2.2.8 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,2-C6H4)OH], 11a in CDCl3

SW : 45.0250 ppm SW_h : 13513.514 Hz

*** Processing Parameters ***

LB : 0.10 Hz 1H WIDE RANGE 45PPM 17/11/98

(ppm) -17.0

(ppm)

2.0 2.1 2.2 2.3 2.4

Figure 2.2.9 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a in CDCl3

7

8

*** Current Data Parameters ***

NAME : FE0311B3 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 128 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz 1H WIDE RANGE 45PPM 17/11/98

(ppm)

Figure 2.2.10 NMR spectrum of Os3(CO)10(μ-H)(μ-SCH2COOH), 13a in CDCl3

*** Current Data Parameters ***

NAME : AG18SHCO EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 16 O1 : 2500.00 Hz PULPROG :

(ppm)

1.5 2.0 2.5 3.0 3.5 4.0

Figure 2.2.11 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a in CDCl3

(ppm)

-17 -16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5

6

7

*** Current Data Parameters ***

NAME : MA0803CR EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 146 O1 : 2500.00 Hz PULPROG :

0 0 0 0.

(ppm) 0.20 0.30 0.40

(ppm)

1.7 1.8 1.9 2.0 2.1 2.2

2 2 2 2 2 2.

(ppm)

2.60 2.70 2.80 2.90 3.00 3.10 3.20

Figure 2.2.12 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)2COOH, 14a(Ru) in CDCl3

(ppm) -15.2

Figure 2.2.13 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a in CDCl3

(ppm)

Figure 2.2.14 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a(Ru) in CDCl3

7.2595 2.3706 2.3211 2.1425 1.7220 1.6726 1.6341 1.5846 1.3813 1.2548 0.9223 0.8811 0.0017 -15.3630

*** Current Data Parameters ***

NAME : AP11RU16 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 64 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz Ru3(CO)12 reflux in toluene with HS(CH2)15COOH

2.8119 3.0312 2.3706 2.3458

(ppm) 2.30 2.40

2.8119 3.0312 2.1672 2.1425 2.1150

(ppm) 2.1 2.2

5.7680 34.719 1.7220 1.6726 1.6341 1.5846

(ppm) 1.6

1.4060 1.3565 1.2548

(ppm) 1.20 1.30

(ppm)

Figure 2.2.15 NMR spectrum of Os3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a in CDCl3

10

*** Current Data Parameters ***

NAME : ma2107 EXPNO : 1 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : spect

NS : 24 O1 : -2250.98 Hz PULPROG : zg30 SFO1 : 300.1277490 MHz

SR : 11.78 Hz 1H(-45ppm)AV300 purified os3sphcooh 1,4 in cdcl3

1.0000 Integral

(ppm) -17.0

(ppm)

0.0 1.0

2.0 3.0

Figure 2.2.16 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a(Ru) in CDCl3

*** Current Data Parameters ***

NAME : ja1507 EXPNO : 1 PROCNO : 1

*** Acquisition Parameters ***

BF1 : 300.1300000 MHz DATE_d : Jan 14 2007 DECNUC : off

NS : 25 NUCLEUS : off PULPROG : zg30 SFO1 : 300.1277490 MHz SOLVENT : CDCl3

(ppm)

Figure 2.2.17 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a in CDCl3

(ppm) -18.0

8

9

*** Current Data Parameters ***

NAME : AP291120 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 24 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz Os3(CO)10HOH+HS(CH2)11COOH band2

Figure 2.2.18 NMR spectrum of Ru3(CO)10(μ-H)2[μ-S(CH2)10COOH], 17a(Ru) in CDCl3

Figure 2.2.19 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a in CDCl3

14

*** Current Data Parameters ***

NAME : AP291630 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 20 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz Os3(CO)10HOH+HS(CH2)15COOH band3

3 3.

(ppm)

3.4 3.6

3.8

2 2.

(ppm) 2.2 2.4

1 1 1 1.

(ppm) 1.2 1.4 1.6 1.8

(ppm)

Figure 2.2.20 NMR spectrum of Ru3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a(Ru) in CDCl3

*** Current Data Parameters ***

NAME : AP26RUSP EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

INSTRUM : AM

NS : 64 O1 : 2500.00 Hz PULPROG :

SR : 3368.00 Hz 1H WIDE RANGE 45PPM 17/11/98

(ppm)

7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1

(ppm) -15.2

Figure 2.2.21.NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)11COOH], 19a in CDCl3

7

8

*** Current Data Parameters ***

NAME : JU011152 EXPNO : 888 PROCNO : 1

*** Acquisition Parameters ***

NS : 40 O2 : 50000.00 Hz SFO1 : 300.1325000 MHz

SW : 45.0250 ppm SW_h : 13513.514 Hz

(ppm) -10.5

1.5846 1.5599 1.5159 1.3895

(ppm) 1.50 1.60 1.70

2.2084 2.1837 2.1590

(ppm) 2.10 2.20

3.6594 3.6155

(ppm) 3.60 3.70

Figure 2.2.22 NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)4OH], 20a in CDCl3

*** Acquisition Parameters ***

D[1] : 1.0000000 sec D[33] : 0.0000000 sec

NS : 8 O2 : 1853.43 Hz SFO1 : 300.1277490 MHz

SW : 45.1479 ppm SW_h : 13550.136 Hz

Figure 2.2.23 NMR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)12OH], 21a in CDCl3

4.8729 32.029

1.5516 1.4555 1.3071

(ppm) 1.2 1.6

(ppm)

Figure 2.2.24.NMR spectrum of [Os3(CO)10(μ-H)(μ-O)]{Si7O10[(CH2)5CH(CH3)2]7}, 28 in CDCl3

1 1 1.

(ppm) 1.08

1 0.

(ppm) 1.00

(ppm) 0.90 440.

Figure 2.2.25.NMR spectrum of [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 in CDCl3

*** Current Data Parameters ***

(ppm) 0.0 0.1 0.2

0.9792 0.9572

(ppm)

0.8 0.9 1.0 1.1

0.6265 0.6031

(ppm) 0.50 0.60 0.70

1.9037 1.8597 1.8142

(ppm) 1.8 2.0

Figure 2.2.26 NMR spectrum of [Os3(CO)10(μ-H)][μ-O(CH2)3Si8O12(i-butyl)7], 30 in CDCl3

(ppm)

3.4 3.6 3.8 4.0 4.2

2.0191 100.30 3.3681 1.9109 1.8888 1.8668 1.8448 1.8213 1.7993 1.5899

(ppm)

1.4 1.6 1.8 2.0 2.2 3.3681 6.0926 627.98 6.0389 195.16 34.048

1.1710 1.1311 1.0911 0.9657 0.8018 0.7563 0.6268 0.5868 0.4752

(ppm)

0.4 0.6 0.8

1.0

1.1710 1.1311 1.0911 0.9657 0.8018 0.7563 0.6268 0.5868 0.4752

(ppm) 0.6 0.8 1.0 1.2

-11.4716 -12.5229 -12.5670 -12.6083 -14.2892

-12.5229 -12.5670 -12.6083

(ppm)

Figure 2.2.27 1H NMR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in CDCl3

*** Current Data Parameters ***

2.6767 2.6299

(ppm) 2.6 2.8 3.8978 738.78

(ppm) 2.0

738.78 1679.0 1.7412 1.7150 1.5772 1.5180 1.4822 1.4643 1.2603

(ppm)

1.2 1.4 1.6 1.8

1.0289 0.9972 0.9641 0.9338

(ppm) 0.8 1.0

0.4888 0.4585 0.4309 0.3992

(ppm) 0.40 0.50

-10.4881 -10.5184

(ppm) -10.5

Figure 2.2.28 31P NMR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in CDCl3

34.6481 -2.2735 -9.8822

(ppm)

-240 -220 -200 -180 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140

*** Current Data Parameters ***

Figure 2.2.29 NMR spectrum of [Os3(CO)10][P(C6H5)2(CH2)2Si8O12(C5H5)7]2, 32b in CDCl3

(ppm) 2.7

(ppm) 1.8

1 1.

(ppm) 1.4

0 0.

(ppm) 1.0

(ppm) 0.2 0.4

(ppm) 0.7

(ppm)

2.3 IR

1980 1990

2000 2020

2040 2060

2080 2100

2120

1/cm 82.5

Figure 2.3.3 IR spectrum of Os3(CO)10(μ-H)[μ-SCH2(1,4-C6H4)CH2SH], 6a in hexane

1970 1980

1990 2000

2020 2040

2060 2080

2100 2120

1/cm -50

Figure 2.3.5 IR spectrum of Os3(CO)10(μ-H)(μ-SC=NNCSS-μ3, η2)Os3(CO)9(μ-H), 8 hexane

1990 2000

2020 2040

2060 2080

2100 2120

Figure 2.3.7 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a in toluene

1990 2000

2020 2040

2060 2080

Figure 2.3.9 NMR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a in toluene

1980 1990

2000 2020

2040 2060

2080 2100

Figure 2.3.11 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)2COOH], 14a in toluene

1965 1980

1995 2010

2040 2070

2020 2040

2060 2080

2100 20

Figure 2.3.13 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,3-C6H4)COOH], 15a in hexane

Figure 2.3.15 IR spectrum of Os3(CO)10(μ-H)[μ-S(1,4-C6H4)COOH], 16a in hexane

1990 2000

2020 2040

2060 2080

2100 2120

1/cm 55

2032.5 2047.5

2062.5 2077.5

2092.5 2107.5

Figure 2.3.17 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a in hexane

1980 1990

2000 2020

2040 2060

2080 2100

2120

1/cm 0

Figure 2.3.19 IR spectrum of Os3(CO)10(μ-H)[μ-S(CH2)15COOH], 18a in hexane

Figure 2.3.21 IR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)11COOH], 19a in hexane

Figure 2.3.23 IR spectrum of Os3(CO)10(μ-H)[μ-O(CH2)12OH], 21a in hexane

Figure 2.3.24 IR spectrum of [Os3(CO)10(μ-H)(μ-O)]{Si7O10[(CH2)5CH(CH3)2]7}, 28 in hexane

1980 1990

2000 2020

2040 2060

2080 2100

2120

1/cm 0

Figure 2.3.25 IR spectrum of [Os3(CO)10(μ-H)][μ-S(CH2)3Si8O12(i-butyl)7], 29 in hexane

1970 1980

1990 2000

2020 2040

2060 2080

2100 2120

bis react with hs-si band1

Figure 2.3.26 IR spectrum of [Os3(CO)10(μ-H)][μ-O(CH2)3Si8O12(i-butyl)7], 30 in hexane

Figure 2.3.27 IR spectrum of [Os3(CO)11][P(C6H5)2(CH2)2Si8O12(C5H5)7], 32a in hexane

1965 1980

1995 2010 2040

2070 2100

2130

1/cm 67.5

mono react with pph2-si band1 (hex) in dcm

Figure 2.3.28 IR spectrum of [Os3(CO)10][P(C6H5)2(CH2)2Si8O12(C5H5)7]2, 32b in hexane

1960 1970

1980 1990

2000 2020

2040 2060

2080 2100

1/cm 94.5

Mass

Figure 2.4.3 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(1,3-C6H4)S], 5b

Figure 2.4.5 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)8SH], 7a

Figure 2.4.7 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)3OH], 10a

Figure 2.4.9 Mass spectrum (positive ion mode) of Os3(CO)10(μ-H)[μ-S(CH2)11OH], 12a

Figure 2.4.11 Mass spectrum positive ion mode) of [Os3(CO)10(μ-H)]2[μ-O(CH2)11S], 12b

Figure 2.4.13 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(1,3-C6H4)COO], 15b

Figure 2.4.15 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(CH2)10COOH], 17b

Figure 2.4.17 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-S(CH2)15COO], 18b

Figure 2.4.19 Mass spectrum (positive ion mode) of[Os3(CO)10(μ-H) [μ-O(CH2)4OH], 20a

Figure 2.4.21 Mass spectrum (positive ion mode) of [Os3(CO)10(μ-H)]2[μ-O(CH2)12O], 21b

Figure 2.4.23 Mass spectrum (positive ion mode) of Ru3(CO)10(μ-H)[μ-S(CH2)10COOH], 17a(Ru)

2.5 Crystal parameter

2.5.1 Crystal parameter for 5a

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Table 3 Bond lengths [Å] and angles [°] for 5a

Table 4 Anisotropic displacement parameters (Å2x 103) for 5a The anisotropic displacement factor exponent

takes the form: -2π2[ h2 a*2U11 + + 2 h k a* b* U12 ]

Table 5 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for 5a

2.5.2 Crystal parameter for 5b

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Table 3 Bond lengths [Å] and angles [°] for 5b

Table 4 Anisotropic displacement parameters (Å2x 103) for 5b The anisotropic

displacement factor exponent takes the form: -2π2[ h2 a*2U11 + + 2 h k a* b* U12 ]

Table 5 Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for 5b

2.5.3 Crystal parameter for 8d

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Table 3 Bond lengths [Å] and angles [°] for 8d