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Development of Synthetic Methodology for Non-Symmetric Fullerene Dimers

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Development of Synthetic Methodology for Non-Symmetric Fullerene Dimers Uppsala University Department of Chemistry - BMC Degree Project C in Chemistry, 1KB010 Development of synthetic methodology for non-symmetric fullerene dimers Author: Fredrik Barn˚a Supervisor: Prof. Helena Grennberg Merve Ergun Donmez¨ June 3, 2019 Abstract This bachelor thesis covers the initial development of a synthesis of fullerene dimers using two different types of linking reactions. Different setups for [3+2] cycloadditions to fullerenes (Prato reaction) were tested, and for that purpose, an N-alkylated amino acid was synthesised. Hydroarylation of fullerene using Rh- catalysis was also studied, using both MIDA protected and unprotected boronic acids, as well as by using cycloaddition products. A range of model compounds in form of fulleropyrrolidenes were synthesised. Products were purified with HPLC and analysed with MALDI-MS and 1H NMR. A range of new compounds were synthesised and characterisation of them was begun. With MALDI-MS, indica- tions that the fullerene dimer had formed were found. Using synthesised model compounds, by-products of the hydroarylation reaction were identified. Sammanfattning Denna kandidatuppsats behandlar p˚ab¨orjandet av syntesutvecklingen f¨or bildan- det av fullerendimerer genom anv¨andandet av tv˚aolika sorters l¨ankningskemi. Oli- ka f¨orh˚allandenoch reagens f¨or [3+2]-cykloaddition till fullerener (Pratoreaktio- nen) studerades, och i samband med det syntetiserades en N-alkylerad aminosyra. Hydroarylering av fullerener med hj¨alp utav rodiumkatalys studerades ¨aven, genom reaktioner med b˚adeskyddade och oskyddade borsyror, inklusive fulleropyrrolidi- ner. Produkter har renats upp med HPLC och analyserats med MALDI-MS och 1H NMR. En upps¨attning nya substanser har syntetiserts, men karakt¨ariseringen av dessa har inte slutf¨orts. Genom anv¨andning av MALDI-MS har indikationer att fullerendimer bildats framkommit. Genom att anv¨anda syntetiserade modell substanser har biprodukter fr˚anhydroaryleringsreaktionen identifierats. 1 Acknowledgements I would like to thank the entire AGHG group for this time, I have learned a lot and have had blast working in the group. 2 Abbreviations and symbols MIDA = N-methyliminodiacetic acid o-DCB = ortho-dichlorobenzene cod = 1,5-cyclooctadiene DCM = dichloromethane MiW = Microwave rb = round bottom MeCN = acetonitrile TFA = triflouroacetic acid TEA = triethylamine MALDI-MS = Matrix Assisted Laser Desorption Ionization Mass Spectrometry HPLC = High Performance Liquid Chromatography t-BuOH = tert-butanol 3 Contents 1 Introduction 5 1.1 Discovery of fullerenes . .5 1.2 The properties and applications for fullerenes . .6 1.3 Reactivity . .7 1.4 Fullerene Dumbbells . .9 1.5 Project aim . .9 2 Results and discussion 10 2.1 Prato reaction with 4-bromobenzaldehyde . 10 2.2 Dumbbell using two Prato reactions . 11 2.3 Prato reaction with 4 and 8 ......................... 12 2.4 Synthesis of 10 ................................ 12 2.5 Prato reaction with N-octylglycine and MIDA ester . 13 2.6 Hydroarylation of C60 with 16 ........................ 15 2.7 Forming the final dumbbell . 15 2.8 Identifying the unknown compounds . 18 3 Conclusions and future outlook 20 4 Experimental 22 4.1 Analysis . 22 4.2 List of reactions in the project . 23 4.3 Synthesis of 5 with the Prato reaction of 3 and 4 ............. 24 4.4 Attempted synthesis of 7 with the Prato reaction of 6 and 4 ....... 24 4.5 Synthesis of 9 with the Prato reaction of 8 and 4 ............. 24 4.6 Synthesis of 10 ................................ 24 4.7 Synthesis of 14 by the Prato reaction with 10 and 8 ........... 25 4.8 Synthesis of 17 by hydroarylation of C60 with 16 ............. 25 4.9 Attempted synthesis of 2 by hydroarylation of C60 with 14 ........ 25 4.10 Treatment of 5 with [Rh(cod)(MeCN)2]BF4 ................ 26 4.11 Synthesis of 21 using the Prato reaction with 10 and 20 ......... 26 4.12 Synthesis of 19 using the Prato reaction with 10 and 18 ......... 26 A Mass spectra 30 B 1H NMR spectra 38 C HPLC chromatograms 42 4 1 Introduction 1.1 Discovery of fullerenes Elemental carbon exists in several different forms, so called allotropes. The two most well known are diamond and graphite, but in the last 40 years, new carbon allotropes have been discovered, such as carbon nanotubes [1], graphene [2] and Buckminsterfullerenes, more often referred to as fullerenes or Buckyballs (see Fig. 1). Figure 1: Newly discovered allotropes of carbon: nanotube, buckminsterfullerene and graphene The concept of a molecule consisting of sixty carbons shaped like a football was first explored in 1965, as a possibility for a hydrocarbon shaped like a geometric solid [3]. In 1970, the existence of such a structure consisting solely of carbon was predicted by Japanese chemists, but as it was never translated in English, it failed to have significant impact [4]. The underlying reasoning behind the prediction was the structure of the corannulene molecule, which has the same structure as a segment of the C60-molecule, and that it might be possible for there to be a fully enclosed molecule. Also in 1970, R.W. Henson, working at the Atomic Energy Research Establishment in the UK, noticed some unexpected patterns in x-ray diffraction measurements on carbon fibres. Based on the different possible structures that could give rise to such a pattern, he realised that the found molecule was the buckminsterfullerene C60. His findings were however never published [5]. In 1973, a computational study on stability of C60 was published, but this was still only theoretical evidence for its existence [6]. In the early 80s, a technique for vaporisation of carbon clusters using lasers was de- veloped by Rickard Smalley and Bob Curl at Rice University, Texas. Harry Kroto, at the university of Surrey, had during the 70s been studying unsaturated carbon chains, and he realised the potential of the new method. He therefore initiated a collaboration between the two groups [7]. The method utilised a Q-switch Nd:YAG laser to quickly vaporise carbon from a graphite target. The hot plasma formed was cooled, and allowed to form clusters of up to a few hundred carbon atoms. Mass spectrometry was then used to study the formed clusters. What was discovered was that the peak corresponding to a m/z-ratio of 720 (which is the weight of sixty carbon atoms) was far more prominent than other ions of similar size, meaning that C60 was for some reason a favoured cluster to form [8]. In their 1985 paper, the group hypothesised that the reason for this was due to the formation of a truncated icosahedron, which they named the "Buckminster- 5 fullerene" after the American architect who popularised the shape [9]. The proposal that the molecule was spherical was not uncontroversial. A strong piece of evidence in favour of the suggested structure came in late 1985, when the group at Rice university managed to create a very stable complex between C60 and a lanthanum atom, arguing that the strong bond was due to the metal atom being enclosed in the fullerene [10], see Fig. 2. Figure 2: Lanthanum atom enclosed in fullerene However, the controversy about the structure of C60 was not yet over, as all evidence of the structure of the molecule was based on intensities of peaks in mass spectro- grams, which some groups argued was not sufficient evidence to infer the structure of the molecule with absolute certainty [11]. It was only in 1990, when a method for the creation of macroscopic amounts of fullerenes was developed, that the truncated icosa- hedron structure was confirmed [12]. In 1996 Kroto, Curl and Smalley were awarded the Nobel Prize in chemistry for their discovery of fullerenes [7]. 1.2 The properties and applications for fullerenes Fullerenes come in many different sizes, where C20 (a regular dodecahedron) up to C150 have been confirmed experimentally, and up to C3998 have been theorised to exist. The two most stable forms of fullerene are C60 and C70, of which C60 is the most common as well as the most studied [13]. Whether C60 is aromatic or not was for a long time subject for debate [14], when it was originally discovered, C60 was presumed to be aromatic [9], but later studies showed that that was not the case. In C60, there are two different types of bonds: 6:6 bonds, that fuse the six-membered rings together, and 6:5 bonds, that lie between the five-member and six-membered rings. These bonds have different characteristics: 6:5 bonds are more alike to single bonds and are of length 1.458A˚ whereas the 6:6 bonds behave more like double bonds and are shorter, 1.439A˚ [13, 15]. The 2:278 2 σ-bond hybridisation in C60 has been calculated to be sp , the deviation from sp - hybridization of graphene being due to the curvature of the molecule[16]. In 1999 de Broglie interference of C60 was observed, which at the time made it the largest and most complicated object for which wave-particle duality had been observed [17]. The electron affinity of C60 has been measured to be 2.65 eV [18], which means that it is highly receptive of additional electrons. Dissolved C60 has a distinct purple colour. It 6 does however only have low solubility in most organic solvents [19]. Fullerenes are insulators, but it is possible, via doping or derivatisation, to turn them into either semiconductors or superconductors. Their unique structure makes it possible to dope fullerenes in three different manners: endohedral, substitutional or exohedral doping. Endohedral doping is a consequence of the unique structure of fullerenes, as it entails one or more atoms being caught inside the fullerene during its formation process. The nomenclature for this uses @, for example, a lanthanum atom (see Fig. 2) enclosed in a C60-molecule would be written La@C60 . In substitutional doping, carbon atoms in the structure are replaced by other atoms, and in exohedral doping, heteroatoms are placed in empty spaces in the lattice [20].
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