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Chapter 1. Introduction Research Collection Doctoral Thesis Alkoxide packaged sodium dihydrogenphosphide synthesis and reactivity Author(s): Hendriksen, Coenradus Johannes Hendrikus Publication Date: 2012 Permanent Link: https://doi.org/10.3929/ethz-a-007333135 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Dissertation ETH No. 20148 Alkoxide Packaged Sodium Dihydrogenphosphide: Synthesis and Reactivity A dissertation submitted to ETH Zurich for the degree of Doctor of Sciences Presented by Coenradus Johannes Hendrikus Hendriksen MSc. Radboud University Nijmegen Born 29th March 1981 Citizen of the Netherlands Accepted on the recommendation of Prof. Dr. H. Grützmacher, examiner Prof. Dr. A. Togni, co-examiner 2012 "Lucifer revealed the shining day and night fled." Ovid, Metamorphoses 8. 1 ff (trans. Melville) (Roman epic C1st B.C. to C1st A.D.) Abstract This work aims to describe the activation of white phosphorus to form highly functionalized compounds. White phosphorus is used as starting material as it is a highly reactive and selective reagent. From white phosphorus new synthesis routes towards sodium dihydrogenphosphide were developed. Previous routes towards sodium dihydrogenphosphide were dangerous and laborious. In this work new procedures are described to synthesize sodium dihydrogenphosphide conveniently at room temperature and apply them on a large scale not requiring high pressures or special equipment. By determining intermediates in the formation of sodium dihydrogenphosphide reaction mechanisms were elucidated. Functionalization of prepared sodium dihydrogenphosphide was of primary interest. In a procedure described by Stein et al. bis(mesitoyl)phosphide was synthesized with sodium dihydrogenphosphide. Although Stein’s route is extremely useful for the synthesis of a wide variety of bis acyl phosphine oxide (BAPO) compounds, low yields in the acylation step resulted in the loss of valuable mesitoyl chloride. Here, a new procedure is described to prepare bis(mesitoyl)phosphide in high yield (80%). Instead of using alkoxide packaged sodium dihydrogenphosphide, a mixture of sodium phosphides was used with tert-butanol (one equivalent compared to phosphorus). This mixture with a reduced amount of sodium tert-butanolate however, keeps the reactivity towards mesitoyl chloride high and selective. Furthermore, other mesitoyl containing compounds were tested for their reactivity towards sodium dihydrogenphosphide of trisodium phosphide. A variety of products is formed and a new sodium bistrityl phosphide compound was synthesized. Interested in the reactivity of alkoxide packaged sodium dihydrogenphosphide as possible precursor for the preparation of sodium pentaphosphacyclopentadienide its reactivity towards white phosphorus was investigated. Sodium pentaphosphacyclopentadienide is an interesting precursor for metal complexes as analogue of the cyclopentadienyl ligand. The synthesis of this phosphorus containing analogue is difficult with low reaction yields (10-20%). Sodium pentaphosphacyclopentadienide in moderate yield (40%) was prepared by the reaction of sodium dihydrogenphosphide with white phosphorus in the presence of benzophenol. In this reaction, benzophenol is reduced by sodium dihydrogenphosphide to diphenylmethanol. Sodium pentaphosphacyclopentadienide is also formed in the reaction of sodium dihydrogenphosphide and benzophenone, although in low yields (<10%). However, trisodium heptaphosphide is formed in 76% yield as an alkoxide packaged cluster. The progress of this reaction was monitored and several intermediates and products have been determined. Other benzophenone, quinone and oxidizing agents have been tested. The reaction of sodium dihydrogenphosphide with benzopinacolone formed Mono Acetyl Phosphine (MAP). This could be confirmed by X-ray analysis. MAP is unstable and decomposes at room temperature when isolated. The applicability of sodium dihydrogenphosphide for the synthesis of metal phosphido complexes was studied in depth to fill gaps in literature. The parent complexes of the phosphido group metal complexes are interesting precursors for the introduction of phosphine groups in organic synthesis. Several nickel carbonyl phosphido complexes were synthesized which however appeared reactive and thus highly unstable. 1) The phosphido nickel complexes react with tetraphenyl phosphonium chloride to form triphenylphosphine, pentaphenylphosphine and other compounds. In contrast, 2) the reaction of iron pentacarbonyl with alkoxide packaged sodium dihydrogenphosphide resulted in the formation of sodium phosphaethynolate (NaOCP). This reaction is very fast and only proceeds when sodium tert- butanolate is present. When 3) sodium dihydrogenphosphide is used, only small amounts of NaOCP are formed, and a large part of iron pentacarbonyl is transformed to Collmans reagent. 4) Addition of extra sodium tert-butanolate resulted in the formation of NaOCP in high yield. Several rhodium phosphido complexes were synthesized, revealing the different binding modes of phosphide as a ligand. These compounds were stable at room temperature under an argon atmosphere. Also a unique rhodium amide compound was synthesized which is the first of its kind for rhodium. This compound is very reactive and insoluble, only X-ray diffraction could establish its formation. Diffusion measurements on [(trop3P)Rh]X complexes revealed the different ion pairing modes of the BArF24, OTf and PF6 anions. Whereas PF6 and OTf are forming a tight ion pair, BArF24 forms a free ion pair. The OTf anion coordinates to the free axial site of the (trop3P)Rh cation, but is easily displaced by better ligands. (trop3P)RhOH is not formed by the addition of water, as reported by Fischbach, however, could be obtained by a direct preparation. Zusammenfassung In dieser Arbeit wird die Aktivierung von weißem Phosphor beschrieben, um hochfunktionalisierte Verbindungen zu bilden. Aufgrund seiner hohen Aktivität und Selektivität wird weißer Phosphor als Startmaterial verwendet. Ausgehend vom weißen Phosphor wurden neue Synthesewege zum Natriumdihydrogenphosphid entwickelt. Frühere Synthesewege zum Natriumdihydrogenphosphid waren abhängig von gefährlichen und laborintensiven Prozeduren. In dieser Arbeit werden neue Wege beschrieben, um Natriumdihydrogenphosphid bequem und bei Raumtemperatur zu synthetisieren. Dieses Verfahren kann auch für große Ansätze und ohne die Verwendung von hohem Druck oder speziellen Apparaturen verwendet werden. Darüber hinaus war es möglich die Reaktion zu verfolgen und Zwischenprodukte bei der Bildung von Natriumdihydrogenphosphid zu bestimmen, was zu einem besseren Verständnis der Reaktion führte. Die Funktionalisierung von synthetisiertem Natriumdihydrogenphosphid wurde untersucht. In einer Vorschrift, beschrieben von Stein et al. wurde „bismesitoyl phosphid“ ausgehend vom Natriumdihydrogenphosphid synthetisiert. Obwohl der von Stein entwickelte Syntheseweg sehr brauchbar in der Synthese einer großen Anzahl von BAPO Verbindungen ist, führen die geringen Ausbeuten im Acetylierungsschritt zum Verlust von wertvollem Mesitoylchlorid. In dieser Arbeit wird eine neue Methode beschrieben, um “bismesitoyl phosphide” in hohen Ausbeuten (80%) zu synthetisieren. Anstelle von Alkoxide packaged Natriumdihydrogenphosphide zu verwenden, wird ein Gemisch aus Natriumphosphide und tert-Butanol (ein Äquivalent im Vergleich zum Phosphor) genommen. Dieses Gemisch, mit einem geringeren Anteil an Natrium-tert-butanolat, hält eine hohe und selektive Reaktivität in Richtung „mesitoyl chloride“. Des Weiteren wurden andere Mesitoyl enthaltende Verbindungen auf ihre Reaktivität in Bezug auf Natriumdihydrogenphosphid oder Natriumphosphid getestet. Eine neue Natriumbistritylphosphidverbindung wurde synthetisiert und eine Anzahl an Produkten konnte gebildet werden. Interessiert an der Reaktivität von Alkoxid packaged Natriumdihydrogenphosphid als möglichen Precursor für die Präparation von Natriumpentaphosphacyclopentadienid, haben wir seine Reaktivität gegen weißen Phosphor untersucht. Natriumpentaphosphacylcopentadienid ist ein interessanter Precursor für Metallkomplexe, als Analogon zu den Cyclopentadienylliganden. Die Synthese dieses phosphorenthaltenden Analogon ist schwierig und die Ausbeuten der Reaktion sind niedrig. Wir konnten Natriumpentaphosphacyclopentadienid in moderaten Ausbeuten (40%), durch die Reaktion von Natriumdihydrogenphosphid mit weissem Phosphor in Anwesenheit von Benzophenol, darstellen. In dieser Reaktion wird Benzophenon durch Natriumdihydrogenphosphid zu Diphenylmethanol reduziert. Selbst die Reaktion von Benzophenon mit Natriumdihydrogenphosphid resultiert in der Bildung von Natriumpentaphosphacyclopentadienid, wenngleich in geringen Ausbeuten. Dennoch wird Trinatriumheptaphosphid in 76% Ausbeute als ein Alkoxid packaged Cluster gebildet. Der Reaktionsfortschritt dieser Reaktion wurde verfolgt und mehrere Zwischenprodukte wurden bestimmt. Andere Benzophenone, Quinone und oxidierende Reagenzien wurden getestet. Die Reaktion von Natriumdihydrogenphosphid mit Benzopinakolon führte zu monoacylphosphin (MAP) und wurde durch Röntgenstrukturanalyse bestimmt. MAP ist instabil und zersetzt sich bei Raumtemperatur, wenn es isoliert wird. Dies wurde zuvor von Liotta beschrieben, jedoch konnten sie die Verbindung nicht isolieren und analysieren. Weitere Untersuchungen von Natriumdihydrogenphosphid
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