In situ spectroscopic of the early events in the rodium mediated pauson khand reaction 2

APPENDIX A EXPERIMENTAL SETUP 243 Appendix A Experimental Setups A.1 High-Pressure Setup Cryostat Figure A.1 High pressure in-situ FTIR apparatus... APPENDIX A EXPERIMENTAL SETUP 244 A

APPENDIX A EXPERIMENTAL SETUP

243

Appendix A Experimental Setups

A.1 High-Pressure Setup

Cryostat

Figure A.1 High pressure in-situ FTIR apparatus

APPENDIX A EXPERIMENTAL SETUP

244

A.2 Low-Pressure Setup

Pressure transducer

Reactor

Liquid Inlet

To FTIR

Pump

Figure A.2 High pressure in-situ FTIR apparatus

A.3 Vertex 70, Bruker MIR spectrometer

APPENDIX A EXPERIMENTAL SETUP

Figure A.4 (a) Close up views of the flow through high pressure Cell and (b)

Cell loaded into the IR compartment

APPENDIX A EXPERIMENTAL SETUP

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

247

Appendix B Fluxionality Of Terarhodium Dodecarbonyl Cluster

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

248

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

249

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

250

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

251

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

252

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

253

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

254

APPENDIX B Fluxionality Of Tetrarhodium Dodecacarbonyl Cluster

255

APPENDIX C Applying DFT to (μ 4 -η 2 -HC 2 H)Co 4 (CO) 8 (μ-CO) 2

256

Appendix C Applying DFT to (μ4-η2-HC2H)Co4(CO)8(μ-CO)2

We carried out DFT calculations to compare predicted and experimental X-ray and the

IR results for (μ4-η2-HC2H)Co4(CO)8(μ-CO)2 [experimental work reported by P L

Stanghellini, Organometallics, 1985, 4, 1612.] Below are (1) the DFT predicted

optimized geometry (2) comparison of predicted and experimental and bond lengths and bond angles and (3) predicted and experimental mid-infrared spectra All are in very good agreement Furthermore, the dihedral angle of butterfly cluster (metal skeleton) is 114.5, see Figure C.1, which compare well with the experimental value of 116

Figure C.1Optimized geometry of (μ 4 -η 2 -HC 2 H)Co 4 (CO) 8 (μ-CO) 2 using DFT with PBE/DGDZVP

APPENDIX C Applying DFT to (μ 4 -η 2 -HC 2 H)Co 4 (CO) 8 (μ-CO) 2

257

Table C.1 Comparison between predicted and experimental (obtained from McNeil and Scholer, 1977)

bond distances (in Å) and angles (in deg) for (μ 4 -η 2 -HC 2 H)Co 4 (CO) 8 (μ-CO) 2

HC 2 H)Co 4 (CO) 8 (μ-CO) 2 using PBE/DGDZVP and the experimentally

observed spectrum after deconvolution.

Table C.2 Predicted and experimental vibrational wavenumbers (cm-1) for (μ 4 -η 2 -HC 2 H)Co 4 (CO) 8 (μ-CO) 2

APPENDIX D RAMAN EXPERIMENTAL SETUP

258

Appendix D Raman Experimental Setup

D.1 Raman Experimental Setup

Figure D.1 Experimental setup for in situ Raman measurements Legend: 1 Argon balloon; 2 Ten mL Schlenk

tube; 3 Stirring plate; 4 Hermetically sealed Teflon Pump; 5 In-house designed flow through Raman cell.

D.2 Schematic Raman Low-Pressure Flow-Through Cell

Figure D.2 Schematic of the flow through Raman cell

APPENDIX D RAMAN EXPERIMENTAL SETUP

259

D.3 Raman microscope (InVia Reflex Renishaw, UK)

Figure D.3 Schematic of the Raman microscope

D.4 Flow-Through Raman Cell Placed Under the Microscope

Figure D.4 The flow-through Raman cell was placed in a Raman microscope under a 5× microscope objective

APPENDIX E Butterfly Cluster

260

Appendix E Butterfly Cluster: Organometallics

APPENDIX E Butterfly Cluster

261

APPENDIX E Butterfly Cluster

262

APPENDIX E Butterfly Cluster

263

APPENDIX E Butterfly Cluster

264

APPENDIX E Butterfly Cluster

265

APPENDIX E Butterfly Cluster

266

APPENDIX F On-Line FTIR Sonochemical Reaction Setup

267

Appendix F On-Line FTIR Sonochemical Reaction Setup

F.1 High-Pressure Setup

1 2

3

4

Figure F.1 Sonochemical apparatus Legend: 1 Ultrasonic power supply; 2 Converter; 3 Membrane pump; 4

Water bath

APPENDIX G Preliminary FIR Analysis

268

Appendix G Preliminary FIR Analysis

The current appendix presents the first attempt of analyzing the far-infrared region The collected spectra were obtain from monitoring the hydroformylation reaction of 3,3-dimethy-l-butene was carried our using Rh4(CO)12 as the catalyst precursor, see scheme G.1

H H

Scheme G.1 Hydroformylation of 3,3-dimethyl-1-butene

G.1 Experimental Setup

The high pressure in-situ FTIR apparatus, described in chapter 3, Section 3.2.2, was used However, the new cell described in chapter 5, section 5.5.1, KRS-5 windows was utilized in order to observe the region 400-1000 cm-1

G.2 Experimental Procedure

First, background spectrum of the purged and empty IR sample chamber was recorded Second, high pressure cell with KRS-5 windows was loaded into the IR compartment of the Perkin-Elmer SPECTRUM 2000 FT-IR spectrometer Third, a 100 mL n-hexane was transferred under argon to the autoclave Under 2 MPa of CO gas, infrared spectra of the n-hexane in the high-pressure cell were recorded Afterward, the stirrer and high-pressure membrane pump were started and a new spectrum was recorded

At the end of the initial steps described above, a solution of circa 50 mg Rh4(CO)9CO)3 dissolved in 50 mL n-hexane was prepared, transferred to the high-pressure reservoir under argon, pressurized and then added to the autoclave After equilibration, infrared spectra of the Rh4(CO)9(μ-CO)3/dissolved gas/n-hexane solution in the high-pressure cell were recorded Afterward, solution of circa 5 mL of 3,3-dimethy-l-but-ene dissolved in 50 mL n-hexane was prepared, transferred to the high-pressure reservoir

(μ-APPENDIX G Preliminary FIR Analysis

269

under argon, pressurized and then added to the autoclave Then, infrared spectra of the

Rh4(CO)9(μ-CO)3/dissolved gas/n-hexane/3,3-dimethy-l-but-ene solution in the pressure cell were recorded

high-Hydroformylation reaction was initiated by introducing 2 MPa of H2 gas Then, spectra were recorded at 10 minute intervals in the range 400-2500 cm-1 The semi-batch experiment lasted 14-hours and circa 70 spectra were collected

APPENDIX G Preliminary FIR Analysis

270

Figure G.2 The deconvoluted spectra of (a) Rh4 (CO) 9 (μ-CO) 3 , (b) RCORh(CO) 4 , (c) ene, and (c) aldehyde.

3,3-dimethyl-1-but-APPENDIX H DFT Improvements

271

Appendix H DFT Improvements

In the current section, the use of an appropriate basis set to describe the coordinated

organic ligands, crabonyls, rather than just using DGDZVP to describe the entire cluster is

investigated This sort of investigation can be computationally expensive, thus, the study

was carried on the relatively simple rhodium carbonyl hydride HRh(CO)4 as shown in

Table H.1

Table H.1 Experimental and calculated vibrational wavenumbers (cm-1) for HRh(CO) 4 and the

corresponding deviation percentage (%) in Italic

6-311++g (3df,3pd) cc-pvqz DGDZVP Expt

It is quiet clear that used of 6-311g (d,p) to describe the organic ligand resulted in

significant improvement in terms of the med-infrared prediction, crica 50% reduction in

error, especially when compared to older calculations as shown in Figure H.1 d Future

work should further investigate wither such improvement can be achieved for larger

clusters and if the new method improve the predicted geometrical parameters as well

APPENDIX H DFT Improvements

272

Figure H.1 Comparison between the theoretically predicted spectrum of HRh(CO)4 using (a) PBE/DGDZVP, (b) PBE/ DGDZVP [Rh]/6-311g (d,p) [C O] and (c) the experimentally observed spectrum after deconvolution.

PUBLICATIONS

273

PUBLICATIONS

International Refereed Journal Articles

Allian, Ayman D and Garland, Marc Spectral resolution of fluxional organometallics

Transactions, 11, pp 1957-1965 2005

Allian, Ayman D.; Tjahjono, Martin and Garland, Marc Reaction of Alkynes with

Allian, Ayman D.; Wang, Yezhong; Saeys, Mark; Kuramshina, Gulnara M and Garland,

Marc The combination of deconvolution and density functional theory for the

mid-infrared vibrational spectra of stable and unstable rhodium carbonyl clusters

Vibrational Spectroscopy, 41(1), pp 101-111 2006

Allian, Ayman D.; Widjaja Effendi and Garland Marc Experimental Raman spectra of

Gao, Feng; Allian, Ayman D.; Zhang, Huajun; Cheng, Shuying and Garland, Marc

Chemical and kinetic study of acetophenone hydrogenation over Pt/Al2O3: Application of BTEM and other multivariate techniques to quantitative on-line FTIR measurements

Journal of Catalysis, 241(1), pp 189-199 2006

Gao, Feng, Ng, Kim Poi; Li, Chuanzhao; Krummel, Karl I.; Allian, Ayman D.; Garland,

Marc A versatile and compact experimental apparatus for the on-line spectroscopic study

of liquid-phase heterogeneous catalytic systems Journal of Catalysis, 237(1), pp 49-57

2006

PUBLICATIONS

274

Tjahjono, Martin; Allian, Ayman D and Garland, Marc The direct determination of

partial molar volumes and reaction volumes in ultra-dilute non-reactive and reactive multi-component systems using a combined spectroscopic and modified response surface

model approach Dalton Transactions, 12, pp 1505-1516 2006

Allian, Ayman D.; Jacub, Chacko and Garland, Marc 13 C NMR study of the butterfly [(μ 4

Allian, Ayman D and Garland, Marc Characterization of the (alkyne)Rh 2 (CO) 6 and

Allian, Ayman D and Garland, Marc Characterization of new class of butterfly cluster;

Allian, Ayman D.; Tjahjono, Martin and Garland, Marc In-situ mid-Infrared Vibrational

in preparation)

Selected Conference Presentations

Garland, Marc; Allian, Ayman D Allian In situ spectroscopic study of the fragmentation

of tetrarhodium dodecacarbonyl under carbon monoxide Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004

Allian, Ayman D.; Wee, Chew Numerical treatment of in-situ data for the pre-catalytic transformations of rhodium carbonyl species and implications AIChE Annual Meeting, Conference Proceedings, Austin, TX, United States, Nov 7-12, 2004

Allian, Ayman D.; Tjahjono, Martin; Garland, Marc Characterization of new rhodium complexes (μ4-η2

-hexyne)Rh4(CO)8(μ -CO)2: In situ FTIR investigation of the reaction of

Rh4(CO)9(μ-CO)3 with monosubstituted/symmetric disubstituted alkynes under Argon and Carbon monoxide Abstracts of Papers, 229th ACS National Meeting, San Diego, CA, United States, March 13-17, 2005

PUBLICATIONS

275

Allian, Ayman D.; Garland, Marc Spectral resolution of fluxional organometallics: Further observations and experimental results for Rh4(CO)9(μ-CO)3 Abstracts of Papers, 229th ACS National Meeting, San Diego, CA, United States, March 13-17, 2005

Allian, Ayman D.; Wang, Yezhong; Saeys, Mark; Garland, Marc Geometrical studies of isolatable and non-isolatable rhodium carbonyl clusters using mid-infrared vibrational spectra and density functional theory Abstracts of Papers, 231st ACS National Meeting, Atlanta, GA, United States, March 26-30, 2006

Allian, Ayman D.; Tjahjono, Martin; Garland, Marc Spectroscopic investigation of the butterfly cluster [(alkyne)Rh4(CO)10] and the kinetic of its formation Abstracts of Papers, 231st ACS National Meeting, Atlanta, GA, United States, March 26-30, 2006

Tjahjono, Martin; Allian, Ayman D.; Li, Chuanzhao; Garland, Marc Direct determination

of the reaction volume of an organometallic reaction at very high dilution AIChE Annual Meeting, Conference Proceedings, Austin, TX, United States, Nov 7-12, 2004

Tjahjono, Martin; Allian, Ayman D.; Garland, Marc Determination of limiting partial molar volumes of some organometallics from high dilution non reactive and reactive multi-component solutions Abstracts of Papers, 229th ACS National Meeting, San

Diego, CA, United States, March 13-17, 2005