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Dipyrazolylphosphanes in Condensation and P–N/P–P Bond Metathesis Reactions

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Dipyrazolylphosphanes in Condensation and P–N/P–P Bond Metathesis Reactions Dipyrazolylphosphanes in Condensation and P–N/P–P Bond Metathesis Reactions DISSERTATION zur Erlangung des akademischen Grades Doctor rerum naturalium (Dr. rer. nat.) vorgelegt dem Bereich Mathematik und Naturwissenschaften der Technischen Universität Dresden von M.Sc. Robin Schoemaker geboren am 05.07.1991 in Nordhorn Eingereicht am 09.06.2020 Verteidigt am 04.09.2020 Gutachter: Prof. Dr. Jan J. Weigand Prof. Dr. Christian Müller Die Dissertation wurde in der Zeit von 11/2015 bis 06/2020 in der Professur für Anorganische Molekülchemie der Technischen Universität Dresden angefertigt. I am very much indebted to Prof. Dr. Jan J. Weigand for his generous support, help and advice. Content 1. Introduction ................................................................................................................... 3 1.1. Pyrazolyl-substituted Phosphanes – Synthesis and Application in Condensation Reactions ........................................................................................................................... 4 1.2. Pyrazolyl-substituted Phosphorus Compounds in Scrambling Reactions .................. 7 1.3. Polyphosphanes in Methylation Reactions ............................................................... 12 1.4. Classification of Pyrazolylphosphanes ..................................................................... 14 2. Objectives .................................................................................................................... 16 3. Synthesis of Pyrazolylphosphanes .............................................................................. 18 3.1. Synthesis of Type II Phosphanes .............................................................................. 18 3.2. Synthesis of Pyrazolyl-substituted Phosphorus Chlorides ....................................... 21 4. Reactivity of Type II Phosphanes towards Secondary Phosphanes ............................ 24 4.1. P–P Bond Formation via Condensation Reactions ................................................... 24 4.2. Coinage Metal Complexes of Triphosphane 48 ....................................................... 26 4.3. P–P Bond Formation via P–N/P–P Bond Metathesis Reactions .............................. 31 4.4. Methylation Reactions of Triphosphane 48 and P–P/P–P Bond Metathesis Reaction ......................................................................................................................................... 35 5. 1,4,2-Diazaphospholium Triflates – Synthesis and Reactivity ................................... 41 5.1. One-Pot Synthesis of 1,4,2-Diazaphospholium Triflate Salts .................................. 43 5.2. Halogenation Reactions of 61[OTf] ......................................................................... 49 Cl2 5.3. Substitution Reactions of 61 [OTf]........................................................................ 53 6. Dipyrazolylphosphanes in Condensation Reactions with Primary Phosphanes .......... 57 6.1. Synthesis of Mixed-substituted Tetraphosphetanes ................................................. 58 6.2. Coinage Metal Complexes of Tetraphosphetane 72 ................................................. 60 6.3. Methylation Reactions of Tetraphosphetanes 71 and 72 .......................................... 64 7. Gold Chloride induced Cleavage of P–P Bonds .......................................................... 71 8. Reactivity studies of Pyridyl-substituted Polyphosphanes towards PdCl2 and PtCl2 .. 79 9. Oxidation of 48 and Subsequent Deprotonation Studies ............................................. 86 10. Summary ................................................................................................................... 91 11. Prospect .................................................................................................................... 96 12. Experimental Details ................................................................................................ 99 12.1. Materials and Methods ........................................................................................... 99 12.2. Syntheses and Characterization Data regarding Compounds in Chapter 3 .......... 101 12.3. Syntheses and Characterization Data regarding Compounds in Chapter 4 .......... 113 12.4. Syntheses and Characterization Data regarding Compounds in Chapter 5 .......... 126 1 12.5. Syntheses and Characterization Data regarding Compounds in Chapter 6 .......... 139 12.6. Syntheses and Characterization Data regarding Compounds in Chapter 7 .......... 149 12.7. Syntheses and Characterization Data regarding Compounds in Chapter 8 .......... 151 12.8. Syntheses and Characterization Data regarding Compounds in Chapter 9 .......... 154 13. Crystallographic Details ......................................................................................... 156 17. Abbreviations ......................................................................................................... 179 18. References .............................................................................................................. 180 19. Acknowledgement .................................................................................................. 193 20. Publications and Conference Contributions ........................................................... 194 20.1. Peer Reviewed Publications ................................................................................. 194 20.2. Oral presentations ................................................................................................. 194 20.3. Poster presentations .............................................................................................. 194 2 1. Introduction Phosphorus plays a crucial role in modern p-block chemistry.1 One reason for that is the diagonal relationship between phosphorus and carbon.2 Comparable to carbon and its chemistry, phosphorus tends to form homoatomic bonds, which is explainable by the relatively high P–P single bond energy (ca. 200 kJ/mol).3 Thus, a plethora of poly- phosphorus compounds are reported in the last decades comprising of fascinating bonding motifs4 and interesting applications in coordination5-7 and synthetic8-11 chemistry, as well as in ligand design.12,13 A crucial point in the chemistry of polyphosphanes is of course the formation of P–P bonds. Numerous synthetic procedures are established and reviewed including salt metathesis,4a,14 dehalosilylation15 and dehalostannylation16 reactions, base promoted dehydrohalogenation reactions17 and dehydrogenative coupling reactions mediated by main group compounds18 or catalysis by transition metals.5,19 Moreover, dialkylamino-substituted phosphanes are used in condensation reactions to form P–P bonds since the early 1960’s. Yet these reactions need elevated temperatures, somewhat limiting the formation of polyphosphorus compounds as stated by the few examples reported.17d,20 The application of pyrazolyl-substituted phosphanes in P–P bond formation reactions is a relatively young field of research.21 Their synthesis and general chemical behavior as well as advantages in comparison to dialkylamino-substituted phosphanes is discussed in the following chapter. 3 1.1. Pyrazolyl-substituted Phosphanes – Synthesis and Application in Condensation Reactions Following the pioneering work by the group of Peterson,22 mainly three synthetic pathways are established for the synthesis of pyrazolyl-substituted phosphanes.23 Reacting 3,5- dimethylpyrazole (1) with phosphorus trichloride in the presence of triethylamine in THF gives the desired tris(3,5-dimethylpyrazolyl)phosphane (2) in 96% yield next to triethylammonium chloride (Scheme 1; I).23a Scheme 1. Synthetic procedures towards pyrazolyl-substituted phosphanes; i) 3 NEt3, -3 [HNEt3]Cl, THF, r.t., 96%; ii) -3 NaCl, THF, 66 °C, 90%; iii) -3 Me3SiCl, neat, r.t., 98%. Sterically encumbered pyrazolyl-substituted phosphanes are accessible via the reaction of phosphorus trichloride with sodium pyrazolide 3 as shown by the synthesis of tris(3,5-di- tert-butylpyrazolyl)phosphane (4) (Scheme 1, II).23b Another convenient way for the formation of 2 is the reaction of PCl3 with 3,5-dimethyl-1-(trimethylsilyl)-pyrazole (5a) (Scheme 1, III).22,23b The solvent free reaction gives 2 in essentially quantitative yields after stirring at ambient temperature and subsequent evaporation of the co-produced trimethylsilylchloride in vacuo. All reported tripyrazolyl-substituted phosphanes are colorless solids that are prone to 23 hydrolysis, but are stable when stored under dry, inert gas, such as N2 or Ar. The necessary exclusion of moisture when working with pyrazolyl-substituted phosphanes indicates their higher reactivity compared to dialkylamino-substituted phosphanes. The latter hydrolyze in 4 the presence of water only slowly,24 and even dialkylamino-substituted phosphanes which are stable towards water, methanol and ethanol are reported.25 Peterson and co-workers further investigated the protolysis of 6 with water or methanol and could proof that it readily gives 1H-pyrazole and diphenyl phosphinous acid or methyl diphenylphosphinite, respectively (Scheme 2).22b Scheme 2. Protolysis of 6 with either water or methanol. Accordingly, the reaction of 6 with sodium methoxide yields methyl diphenylphosphinite and sodium pyrazol-1-ide. In a similar fashion, reacting 6 with phenyllitihum yields Ph3P and lithium pyrazol-1-ide.22b Such exchange reactions are also observed for 2 with Grignard reagents (RMgX, R = Me, Ph; X =
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