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Part A: Organoplatinum(II) Complexes with Bridging bis(Diphenylphosphino)ethane or Monodentate Benzo[h]quinolyl Ligands Part B: Selectivity in Metal–Carbon Bond Protonolysis in Cycloplatinated(II) Complexes

Name: Part A: Organoplatinum(II) Complexes with Bridging bis(Diphenylphosphino)ethane or Monodentate Benzo[h]quinolyl Ligands Part B: Selectivity in Metal–Carbon Bond Protonolysis in Cycloplatinated(II) Complexes
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Ph.D. DISSERTATION IN

INORGANIC CHEMISTRY

Part A: Organoplatinum(II) Complexes with Bridging bis(Diphenylphosphino)ethane or Monodentate Benzo[h]quinolyl Ligands

Part B: Selectivity in Metal–Carbon Bond Protonolysis in Cycloplatinated(II) Complexes

In part A, cyclometalated complexes [Pt(ppy)R(SMe₂)] or [Pt(bhq)R(SMe₂)], where ppyH = 2-phenylpyridine or bhqH = benzo[h]quinoline and R = methyl or p-tolyl, react with bis(diphenylphosphino)ethane, dppe, in a 1 : 1 ratio to give the corresponding complexes [Pt(κ¹–C-ppy)R(dppe)], 1-2, or [Pt(κ¹–C-bhq)R(dppe)], 3, in which the ppy or bhq ligands are monodentate and dppe is chelating. The similar reaction in a 2 : 1 ratio gives the binuclear complexes [Pt₂(ppy)₂R₂(µ-dppe)], 4 & 6, or [Pt₂(bhq)₂R₂(µ-dppe)], 5 & 7, in which the dppe ligands are in the unusual bridging bidentate bonding mode.

In Part B, Reaction of each of the known starting complexes [PtR(C^N)(SMe₂)] with one equivalent of CF₃CO₂H, gave the complexes [Pt(C^N)(CF₃CO₂)(SMe₂)], 8–9. The bis-chelate complexes [Pt(C^N)(P^P)](CF₃CO₂), 14–17, were obtained by reaction of complexes [Pt(C^N)(CF₃CO₂)(SMe₂)], 8–9, with one equivalent of either of the P^P bisphosphine reagents, dppf = 1,1’-bis(diphenylphosphino)ferrocene or dppe. In contrast with the reaction with dppe, when the complex [Pt(bhq)(CF₃CO₂)(SMe₂)], 9, was reacted with 0.5 equivalents of dppf, then the binuclear complex [Pt₂(bhq)₂(CF₃CO₂)₂(μ-dppf)], 18, formed in pure form. In all the above-mentioned acid reactions, the M–R bond rather than the M–C bond of the cycloplatinated complex is cleaved. When the complexes [PtR(C^N)PPh₃] in which C^N is ppy or tpy = deprotonated 2-p-tolylpyridine, were reacted with one equivalent of CF₃CO₂H, the course of the reaction reversed and the M–C bonds of the cycloplatinated complexes are cleaved rather than the M–R bonds. The latter reaction gave [PtR(κ¹–N-HC^N)(PPh₃)(CF₃CO₂)], 10–12, as an equilibrium mixture of two isomers. Crystal structures of the typical complexes show a variety of extensive intermolecular hydrogen bonding involving C–H bonds from the different ligands and electronegative atoms (O or F) from the CF₃CO₂¯ moiety. On the basis of data obtained from kinetic studies (using ¹H-NMR spectroscopy), a dissociative mechanism is proposed for the case of isomerization process, involving dissociation of the κ¹–N-Htpy neutral ligand, rather than the alternative route of PPh₃ or CF₃CO₂¯ ligand dissociation.

دسته: زبان خارجه, زبان خارجه برچسب: Part A: Organoplatinum(II) Complexes with Bridging bis(Diphenylphosphino)ethane or Monodentate Benzo[h]quinolyl Ligands, Part B: Selectivity in Metal–Carbon Bond Protonolysis in Cycloplatinated(II) Complexes

توضیحات

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Part A: Organoplatinum(II) Complexes with Bridging bis(Diphenylphosphino)ethane or Monodentate Benzo[h]quinolyl Ligands 2

Chapter One: Introduction and Literature Review.. 3

Table of Figures

Figure A.1.1. Orbital interaction in metal-alkyl bond…………………………..….5

Figure A.1.2. Bridging alkyl in Al₂Me₆………………………………………..…..6

Figure A.1.3. syn- and anti- forms of trans-[Pt(PEt₃)₂(o-MeC₆H₄)₂]…………..…10

Figure A.1.4. Some typical phosphine ligands……………………………………10

Figure A.1.5. Shading represents orbital occupation…………………………….12

Figure A.1.6. Electronic and steric effects of common P-donor ligands plotted on a map according to Tolman…………………………………………13

Figure A.1.7. Some platinum complexes with bridging dppe ligands…………….19

Figure A.3.1. ¹H-NMR spectrum of mixture cis/trans-[PtCl₂(SMe₂)₂] in CDCl₃…42

Figure A.3.2. ¹H NMR spectrum of [Me₂Pt(m-SMe₂)₂PtMe₂] in CDCl₃………….44

Figure A.3.3. ¹H-NMR spectrum of cis-[Pt(p-MeC₆H₄)₂(SMe₂)₂] in CDCl₃……..47

Figure A.3.4. ¹H-NMR spectrum of [Pt(Me)(ppy)(SMe₂)] in CDCl₃……………..49

Figure A.3.5. ¹H-NMR spectrum of [Pt(Me)(bhq)(SMe₂)] in CDCl₃……………..51

Figure A.3.6. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(ppy)(SMe₂)] in CDCl₃………53

Figure A.3.7. The crystal structure, aggregation and crystal packing of [Pt(p-MeC₆H₄)(ppy)(SMe₂)]…………………………………………54-55

Figure A.3.8. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(bhq)(SMe₂)] in CDCl₃………57

Figure A.3.9. ¹³C{¹H}-NMR spectrum of [Pt(p-MeC₆H₄)(bhq)(SMe₂)] in CDCl₃..59

Figure A.3.10. Expansion of ¹³C{¹H}-NMR spectrum of [Pt(p-MeC₆H₄)(bhq)(SMe₂)] in CDCl₃………………………………….60

Figure A.3.11. The crystal structure, aggregation and crystal packing of complex [Pt(p-MeC₆H₄)(bhq)(SMe₂)]…………………………………..61-62

Figure A.3.12. ¹H-NMR spectrum of [Pt(Me)(κ¹–C-ppy)(dppe)], 1, in CDCl₃……64

Figure A.3.13. ³¹P{¹H}-NMR spectrum of [Pt(Me)(κ¹–C-ppy)(dppe)], 1, in CDCl₃………………………………………………………….…66

Figure A.3.14. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(κ¹–C-ppy)(dppe)], 2, in C₆D₆………………………………………………………………68

Figure A.3.15. ³¹P{¹H}-NMR spectrum of [Pt(p-MeC₆H₄)(κ¹–C-ppy)(dppe)], 2, in CDCl₃…………………………………………………………….70

Figure A.3.16. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(κ¹–C-bhq)(dppe)], 3, in C₆D₆………………………………………………………………73

Figure A.3.17. ³¹P{¹H}-NMR spectrum of [Pt(p-MeC₆H₄)(κ¹–C-bhq)(dppe)], 3, in CDCl₃…………………………………………………………….75

Figure A.3.18. Views of the DFT calculated structure and the HOMO of [Pt(p-MeC₆H₄)(κ¹–C-bhq)(κ²–P,P-dppe)]……………………………..…76

Figure A.3.19. ¹H-NMR spectrum of [Pt₂(Me)₂(ppy)₂(m-dppe)], 4, in CDCl₃…….78

Figure A.3.20. ³¹P{¹H}-NMR spectrum of [Pt₂(Me)₂(ppy)₂(m-dppe)], 4, in CDCl₃…………………………………………………………….80

Figure A.3.21. ¹H-NMR spectrum of [Pt₂(Me)₂(bhq)₂(m-dppe)], 5, in CDCl₃….82

Figure A.3.22. ³¹P{¹H}-NMR spectrum of [Pt₂(Me)₂(bhq)₂(m-dppe)], 5, in CDCl₃…………………………………………………………….84

Figure A.3.23. ¹H-NMR spectrum of [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)], 6, in CDCl₃…………………………………………………………….86

Figure A.3.24. ³¹P{¹H}-NMR spectrum of [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)], 6, in CDCl₃…………………………………………………………….88

Figure A.3.25. The Crystal structure, aggregation and crystal packing of [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)], 6………………………………….89-90

Figure A.3.26. ¹H-NMR spectrum of [Pt₂(p-MeC₆H₄)₂(bhq)₂(m-dppe)], 7, in CDCl₃…………………………………………………………….93

Figure A.3.27. ³¹P{¹H}-NMR spectrum of [Pt₂(p-MeC₆H₄)₂(bhq)₂(m-dppe)], 7, in CDCl₃…………………………………………………………….95

Figure A.3.28. The crystal structure, aggregation and crystal packing of [Pt₂(p-MeC₆H₄)₂(bhq)₂(m-dppe)],7……………………………………96-97

Figure A.3.29. The calculated structures of (a) [Pt(Ph)(κ²–C,N-ppy)(κ¹–P-dppe)] and (b) [Pt(Ph)(κ¹–C-ppy)(κ²–P,P-dppe)]………………………..……99

Figure A.3.30. The calculated structures of (a) [Pt(Ph)(κ²–C,N-bhq)(κ¹–P-dppm)] and (b) [Pt(Ph)(κ¹–C-bhq)(κ²–P,P-dppm)]……………………..…99

Figure B.1.1. The types of cyclometalation reactions………………………..….109

Figure B.1.3. Cyclometalation reactions…………………………………………111

Figure B.1.4. Some example of ortho-metalation complexes…………………..111

Figure B.1.5. Cyclometalation reaction with heat……………………………….112

Figure B.1.6. Benzo-fused heterocycles ligands……………………….…….…113

Figure B.1.7. Example of six-membered cyclometalated complexes………….116

Figure B.1.8. Mechanisms of Cyclometalation reactions………………………..117

Figure B.1.9. Electronic effects of meta-substitution……………………………119

Figure B.1.10. Addition-Elimination mechanism……………………………….120

Figure B.1.11. Example of some cyclopalladated reactions……………………..121

Figure B.1.12. Cyclometalation of the Platinum Metals with Nitrogen…………122

Figure B.1.13. C-H Activation by Pt Complexes………………………………..124

Figure B.1.14. Shilov catalytic system…………………………………………..127

Figure B.1.15. Oxidation of alkanes to alcohols…………………………………128

Figure B.3.1. ¹H-NMR spectrum of [Pt(Me)(ppy)(PPh₃)] in CDCl₃……………..146

Figure B.3.2. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(ppy)(PPh₃)] in CDCl₃………148

Figure B.3.3. ¹H-NMR spectrum of [Pt(Me)(tpy)(PPh₃)] in CDCl₃………………150

Figure B.3.4. ¹H-NMR spectrum of [Pt(ppy)(CF₃CO₂)(SMe₂)], 8, in CDCl₃……152

Figure B.3.5. ¹H-NMR spectrum of [Pt(bhq)(CF₃CO₂)(SMe₂)], 9, in CDCl₃……154

Figure B.3.6. The crystal structure, aggregation and crystal packing of [Pt(bhq)(CF₃CO₂)(SMe₂)], 9……………………………….155-156

Figure B.3.7. ¹H-NMR spectrum of [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10, in CDCl₃……………………………………………………………160

Figure B.3.8. ³¹P{¹H}-NMR spectrum of [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10, in CDCl₃…………………………………………………………162

Figure B.3.9. Crystal structure, aggregation and crystal packing of [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10a…………………………………163-164

Figure B.3.10. ¹H-NMR spectrum of [Pt(p-MeC₆H₄)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 11, in CDCl₃……………………………………………………..168

Figure B.3.11. ³¹P{¹H}-NMR spectrum of Pt(p-MeC₆H₄)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 11, in CDCl₃…………………………..170

Figure B.3.12. ¹H-NMR spectrum of [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12, in CDCl₃……………………………………………………………173

Figure B.3.13. ³¹P{¹H}-NMR spectrum of [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12, in CDCl₃…………………………………………………………175

Figure B.3.14. Crystal structure, aggregation and crystal packing of [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12a…………………………………176-177

Figure B.3.15. Calculated structures and relative energies for [PtMe(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10a, and its first dissociation step….…180

Figure B.3.16. Monitoring the 12a/12b isomerization process by ¹H NMR spectroscopy (in the aliphatic region) in CDCl₃ at 25°C…………181

Figure B.3.17. Changes in molar concentration versus time during equilibrium formation involving the isomerization process of 12a to 12b in CDCl₃……………………………………………………………182

Figure B.3.18. Monitoring the 12a/12b isomerization process by ¹H NMR spectroscopy (in the aliphatic region) in C₆D₆at 25°C…………..184

Figure B.3.19. Changes in molar concentration versus time during equilibrium formation involving the isomerization process of 12a to 12b in C₆D₆……………………………………………………………..184

Figure B.3.20: ¹H-NMR spectrum of [Pt(ppy)(PPh₃)(CF₃CO₂)], 13, in CDCl₃…187

Figure B.3.21: ³¹P{¹H}-NMR spectrum of [Pt(ppy)(PPh₃)(CF₃CO₂)], 13, in CDCl₃……………………………………………………………189

Figure B.3.22. ¹H-NMR spectrum of [Pt(ppy)(dppe)][CF₃CO₂], 14, in CDCl₃…..192

Figure B.3.23. ³¹P{¹H}-NMR spectrum of [Pt(ppy)(dppe)][CF₃CO₂], 14, in CDCl₃……………………………………………………………194

Figure B.3.24. ¹H-NMR spectrum of [Pt(bhq)(dppe)][CF₃CO₂], 15, in CDCl₃…..197

Figure B.3.25. ³¹P{¹H}-NMR spectrum of [Pt(bhq)(dppe)][CF₃CO₂], 15, in CDCl₃……………………………………………………………199

Figure B.3.26. The crystal structure, aggregation and crystal packing of [Pt(bhq)(dppe)][CF₃CO₂], 15……………………………….200-201

Figure B.3.27. ¹H-NMR spectrum of [Pt(ppy)(dppf)][CF₃CO₂], 16, in CDCl₃…..204

Figure B.3.28. ³¹P{¹H}-NMR spectrum of [Pt(ppy)(dppf)][CF₃CO₂], 16, in CDCl₃……………………………………………………………206

Figure B.3.29. ¹H-NMR spectrum of [Pt(bhq)(dppf)][CF₃CO₂], 17, in CDCl₃…..209

Figure B.3.30. ³¹P{¹H}-NMR spectrum of [Pt(bhq)(dppf)][CF₃CO₂], 17, in CDCl₃……………………………………………………………211

Figure B.3.31. ¹H-NMR spectrum of [Pt₂(bhq)₂(CF₃CO₂)₂(µ-dppf)], 18, in CDCl₃……………………………………………………………214

Figure B.3.32. ³¹P{¹H}-NMR spectrum of [Pt₂(bhq)₂(CF₃CO₂)₂(µ-dppf)], 18, in CDCl₃……………………………………………………………216

List of Tables

Table A.2.1. Crystal data and structure refinement for [Pt(p-MeC₆H₄)(ppy)(SMe₂)]……………………………………………..32

Table A.2.2. Crystal data and structure refinement for [Pt(p-MeC₆H₄)(bhq)(SMe₂)]……………………………………………..33

Table A.2.3. Crystal data and structure refinement for [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)].2/3 CH₂Cl₂, 6………………………………………………34

Table A.2.4. Crystal data and structure refinement for [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)].2 CH₂Cl₂, 7………………………………………………..35

Table A.3.1. Selected bond lengths [Å] and angles [°] for [Pt(p-MeC₆H₄)(ppy)(SMe₂)]……………………………………………55

Table A.3.2. Selected bond lengths [Å] and angles [°] for [Pt(p-MeC₆H₄)(bhq)(SMe₂)]……………………………………………62

Table A.3.3. Selected bond lengths [Å] and angles [°] for [Pt₂(p-MeC₆H₄)₂(ppy)₂(m-dppe)], 6……………………………………………………………91

Table A.3.4. Selected bond lengths [Å] and angles [°] for [Pt₂(p-MeC₆H₄)₂(bhq)₂(m-dppe)], 7…………………………………………………………..97

Table B.2.1. Crystal data and structure refinement for [Pt(bhq)(CF₃CO₂)(SMe₂)], 9…………………………………………………………………139

Table B.2.2. Crystal data and structure refinement for [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10a……………………………………..140

Table B.2.3. Crystal data and structure refinement for [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12a……………………………….…….141

Table B.2.4. Crystal data and structure refinement for [Pt(bhq)(dppe)]CF₃CO₂, 15………………………………………………………….…….142

Table B.3.1. Selected bond lengths [Å], angles and torsion angles [°] for [Pt(bhq)(CF₃CO₂)(SMe₂)], 9……………………………………157

Table B.3.2. Hydrogen bonds for [Pt(bhq)(CF₃CO₂)(SMe₂)], 9 [Å and °]………157

Table B.3.3. Bond lengths [Å], angles and torsion angles [°] for [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10a……………………………………..165

Table B.3.4. Hydrogen bonds for [Pt(Me)(κ¹N-Hppy)(PPh₃)(CF₃CO₂)], 10a [Å and °]…………………………………………………………………165

Table B.3.5. Bond lengths [Å], angles and torsion angles [°] for [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12a………………………………………178

Table B.3.6. Hydrogen bonds for [Pt(Me)(κ¹N-Htpy)(PPh₃)(CF₃CO₂)], 12a [Å and °]…………………………………………………………………178

Table B.3.7. Data for the equilibrium formation between isomers 12a and 12b at 25°C……………………………………………………………..183

Table B.3.8. Bond lengths [Å], angles and torsion angles [°] for [Pt(bhq)(dppe)][CF₃CO₂], 15…………………………………….202

Table B.3.9. Hydrogen bonds for [Pt(bhq)(dppe)][CF₃CO₂], 15 [Å and °]…………………………………………………………………