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Late Transition Metal Complexes of Pentafluorophenylphosphino

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Late Transition Metal Complexes of Pentafluorophenylphosphino Late Transition Metal Complexes of Pentafluorophenylphosphino- Pincer Ligands by Bradley George Anderson A thesis submitted to Victoria University of Wellington in fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry Victoria University of Wellington 2012 Abstract This thesis details the synthesis of new examples of electron-poor pincer ligands, fea- turing bis(pentafluorophenyl)phosphine donors attached to 1,3-substituted pheny- lene or 2,6-substituted pyridine backbones, to create tridentate PCP and PNP lig- ands. The effect of the ligands’ electronic nature on the coordination chemistry and ease of pincer complex synthesis with late transition metals is discussed, as is the catalytic activity of the resultant palladium pincer complexes in the Heck and Suzuki reactions. Symmetric PCP and PNP ligands possessing bis(pentafluorophenyl)phosphinite and bis(pentafluorophenyl)phosphoramine functionalities were synthesised by reaction of bis(pentafluorophenyl)phosphine bromide with resorcinol, 3-hydroxybenzyl-di- tert-butylphosphine, 2,6-diaminopyridine, or 2,6-dihydroxypyridine, affording 1,3- t [(C6F5)2PO]2C6H4 (POCOPH, 1), 1-[(C6F5)2PO]-3-( Bu2PCH2)2C6H4 (POCCPH, 3), 2,6-[(C6F5)2PNH]2C6H3N (PNNNP, 10), and 2,6-[(C6F5)2PO]2C6H3N (PONOP, 11) respectively. The previously reported 1,3-[(C6F5)2PCH2]2C6H4 (PCCCPH, 2) was also synthesised, with the literature yield improved upon by the use of magnesium-anthracene to generate the required Grignard reagent. The coordination chemistry of the POCOPH ligand 1 with platinum(0) alkene and platinum(II) dimethyl precursors revealed an affinity for the formation of cis-bridged oligomeric structures. The dimer [(POCOPH)Pt(nb)]2 (14, nb = norbornene) was isolated and crystallographically characterised from the reaction between 1 and [Pt(nb)3]. The solid state structure revealed the presence of stabilising π-π interac- tions between the aromatic ligand backbones, which were also observed in solution by 1H NMR spectroscopy. Reactions of ligand 1 with platinum and palladium dichlo- ride or chloromethyl starting materials led to rare examples of cis,trans-dimers of the type cis,trans-[(POCOPH)MClX]2 (M = Pd, Pt; X = Cl, Me). In part due to facile dimer formation with 1, metallation of the ligand backbone to form the tridentate pincer complex [(POCOP)PtCl] (25) required long reaction times and high temperatures. It was observed that platinum dichloride starting materials with ii more strongly binding ancillary ligands were less prone to oligomer formation, and could facilitate more rapid metallation to from 25. More facile pincer complex for- mation was also observed for more electron-rich ligands with both PCP and PNP pincer ligands. The electron poor platinum and palladium POCOP, PCCCP, and POCCP pin- cer complexes (where the free ligand had been deprotonated upon metallation) were synthesised and subsequently converted into the metal carbonyl species [(PCP)M(CO)]+. Analysis of C O stretching frequencies by infrared spectroscopy − confirmed complexes of POCOP ligand 1 were the most electron poor, while those of POCCP ligand 3 were the most electron rich. Decarbonylation of the palladium pincer complexes was observed in solution and in the solid state, and was more facile for complexes with a higher wavenumber C O stretch. − Reaction of the [(PCP)PtCl] pincer complexes with methyl nucleophiles revealed that treatment with methylmagnesium iodide resulted in halide exchange, while methyllithium promoted nucleophilic attack at phosphorus. Spectroscopic data in- dicated that in one instance this led to pentafluorophenyl migration to the metal centre to form a [(PCP)Pt(C6F5)] complex. Dimethylzinc was successful in methy- lating the platinum PCP complexes; however, it was observed to degrade the pal- ladium PCP pincer complexes. Treatment of the rhodium PNP pincer complex [(PNNNP)RhCl] (49) with dimethylzinc also resulted in degradation, which spec- troscopic evidence indicated proceeded via ligand deprotonation and the formation of a zinc adduct of 49. Low temperature protonolysis of the [(PCP)PtMe] species did not reveal any information about possible interactions between the metal and liberated methane. The catalytic activity of the electron-poor [(PCP)PdCl] complexes were assessed in the Heck and Suzuki cross-coupling reactions. The complexes of 1, 2, and 3 were all found to possess only modest activity in the Heck reaction, functioning as precatalysts which decomposed to give catalytically-active Pd(0) colloids. Under milder Suzuki reaction conditions, the most electron-poor complex, [(POCOP)PdCl] (28) proved to be one of the most active pincer catalysts known for this reaction, able to achieve a turnover number of 176,000 for the coupling of electronically-deactivated aryl bromides and phenylboronic acid. Mercury poisoning tests revealed that Suzuki reactions catalysed by 28 proceeded via a homogeneous active species. iii Acknowledgments Thanks to the boss, Prof. John L. Spencer. Your support, guidance, and experience has been much appreciated during this interesting, challenging, tough and testing time. Thanks to Mum, Dad, and Gran; your enthusiastic support for me in my scholastic endeavours has always been a source of motivation. Cheers to all of the Spencer group members, past and present; Almas, Chris, David, Jacqui, Kathryn, Melanie, Sarah, Teresa. I am especially grateful to Almas and Kathryn for their assistance in developing some half-decent lab skills during my formative years in chemical research. Thanks to Dr. John Ryan, Ian Vorster, Dr. Robert Keyzers, and Dr. Jono Singh for their assistance with NMR spectroscopy and mass spectrometry. Cheers to Emma for being a better rhodium chemist than me. Thanks to the SPCS administrative and technical stuff; you guys keep the School running smoothly and have made all the little surprises that come with doing research a bit easier to deal with. Thanks to the CMFC for an increased appreciation of appropriately aged distillates (especially their rheological properties). Thanks those to whom I’ve talked to about work, your advice and feedback was appreciated. Finally, cheers to the jokers who I’ve called mates, you’ve helped keep me sane. It can’t have been easy. iv Table of Contents Abstract ii Acknowledgments iv Table of Contents v List of Figures viii List of Schemes x List of Tables xii Glossary xiii 1 Introduction 1 1.1 Metal-LigandCoordinationComplexes . .. 1 1.2 PincerComplexes............................. 2 1.2.1 Uses of Pincer Complexes With Phosphorus Donors . 5 1.3 Electron-PoorLigands . 7 1.3.1 Electron-PoorPincerComplexes. 9 1.4 SynthesisofPCPandPNPPincerComplexes . 10 1.5 Palladium-CatalysedCross-Coupling . ... 14 1.6 ResearchObjectives. 15 1.7 ConcludingRemarks ........................... 15 2 Ligand Synthesis 17 2.1 Synthesis of Pentafluorophenyl-Substituted PCP Pincer Ligands . 19 2.2 Synthesis of Pentafluorophenyl-Substituted PNP Pincer Ligands . 25 2.3 Attempted Synthesis of Trifluoromethylaryl-SubstitutedLigands . 26 2.4 ConcludingRemarks ........................... 27 3 CoordinationChemistryofPCPPincerLigands 29 3.1 HistoricalOverview............................ 29 3.2 CoordinationtoPt(0) . 31 3.3 CoordinationtoPt(II) . 38 v 3.3.1 Reactions with [PtMe2(1,5-hexadiene)] . 38 3.3.2 Reactions with [PtCl2(1,5-hexadiene)]. 42 3.3.3 Reactions with [PtClMe(1,5-hexadiene)] . .. 49 3.3.4 Reactions with [PdCl2(NCMe)2]................. 53 3.3.5 Literature Precedent for cis,trans-Dimers. 57 3.4 ConcludingRemarks ........................... 58 4 SynthesisandReactivityofPCPPincerComplexes 61 4.1 SynthesisofPCPPincerComplexes. 61 4.1.1 Effect of Metal Precursor on PCP Pincer Synthesis . 62 4.1.2 EffectoftheLigandonPCPPincerSynthesis . 66 4.2 ReactionsofPt/PdPincerCompounds . 68 4.2.1 Synthesis of Pincer Metal-Carbonyl Compounds . .. 68 4.2.2 Methylation of Pincer Chloride Complexes . 80 4.2.3 Protonation of Platinum Methyl Complexes . 87 4.3 ConcludingRemarks ........................... 88 5 SynthesisandReactivityofPNPPincerComplexes 90 5.1 SynthesisofPlatinumPNPComplexes . 91 5.2 SynthesisofRhodiumPNPSpecies . 94 5.3 ConcludingRemarks . .104 6 CatalyticActivityofPalladiumPincerComplexes 106 6.1 PalladiumPincerComplexesinCatalysis . .106 6.2 Mechanistic Implications of Catalysis with PCP Pincer Complexes . 107 6.3 Performance of [(PCP)PdCl] Species in the Heck Reaction . .110 6.3.1 ResultsofHeckReactions . .111 6.3.2 Active Species Generation and Reaction Mechanism . 115 6.4 Performance of [(PCP)PdCl] Species in the Suzuki Reaction . .120 6.4.1 ResultsofSuzukiReactions . .121 6.4.2 Active Species Generation and Reaction Mechanism . 129 6.5 Concludingremarks. .140 7 Conclusions 143 8 Experimental 147 8.1 GeneralProcedures . .147 8.2 TransitionMetalPrecursors . 148 8.3 Ligands ..................................150 8.4 PlatinumComplexes . .153 8.5 PalladiumComplexes. .165 8.6 RhodiumComplexes . .171 vi 8.7 CatalyticTesting .............................174 References 177 vii List of Figures 1.1 Examplesofpincerligandstructures. ... 3 1.2 Outlineofthealkanemetathesisreaction. .... 6 1.3 Outline of water splitting by pincer complexes. ...... 7 1.4 Electronic effects of phosphorus substituents. ....... 8 1.5 Electronic influence on transfer-dehydrogenation catalysis. ...... 9 1.6 Facially-coordinated, electron-poor PCP pincer complexes ...... 10 3.1 ORTEP diagram of [(POCOPH)Pt(nb)] 2 CH Cl (14)........ 33 2 · 2 2 3.2 ORTEP diagram of [(POCOPH)Pt(nb)] 2 CH Cl (14)........ 36 2 · 2 2 3.3 Effect of π-π stacking on the 1H NMR data of compounds
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