Indiana University-Purdue University Indianapolis (IUPUI) / Mononuclear molybdopterin enzymes are a large class of enzymes that are present in all phyla of life. All pterin containing enzymes posses a molybdopterin cofactor made up of a molybdenum metal center coordinated directly by a dithiolene ligand, which is appended to a pyranopterin cofactor. The majority of these enzymes catalyze oxygen atom transfer reactions that are concomitant with a transfer of two-electrons. We are hypothesizing that by altering the oxidation states of the dithiolene, the reactivity of the cofactor can be tuned for different substrates. This investigation focuses on the synthesis and characterization of oxo-MoIV(dithiolene) complexes that possess a fully reduced dithiolene ligand (dithiolene) and a fully oxidized dithiolene ligand (dithione). These complexes are designed to represent the asymmetry of the dithiolene ligand that is observed in the crystal structures of the DMSO reductase family. Asymmetric oxo-MoIV(dithiolene) complexes exhibit a unique structural property, a large fold angle along the S•••S vector of the dithione ligand. These complexes also show a positive solvatochromic effect in a range of polar to nonpolar solvents. The rich electrochemical properties of these redox active complexes and other characterization details such as IR, and NMR studies will be presented. Effects on the reactivity of these complexes using biologically relevant substrates will be discussed. The oxygen atom transfer reactivity has been probed by mass spectrometry and NMR spectroscopy. The presented complexes aide in highlighting the effect redox state of the dithiolene ligand has in modulating reactivity

A series of new planar complexes with the dianion of 2,3-quinoxalinedithiol ligand has been prepared. The complexes have been characterized from the study of their analyses, magnetic moment, conductance, polarograms, electron spin resonance spectra, and electronic spectra, and compared with the available data on the corresponding maleonitriledithiolene and toluene-3,4-dithiolene complexes.

The field of organic, or molecular, electronics is currently dominated by both polymeric and molecular organic materials, while considerably less research efforts are devoted to transition metal based complexes. Despite this, such compounds can offer advantages including additional tuneability of the spatial distribution and energy levels of the frontier orbitals or stable paramagnetic species by manipulating the metal-ligand interactions which may be accomplished selectively modifying the ligand framework or changing the central metal. A series of Ni(II) and Cu(II) acenaphthenequinone bis(thiosemicarbazonato) complexes were prepared and characterised using X-ray diffraction, cyclic voltammetry, UV/Vis and EPR spectroscopy, as well as magnetic susceptibility and field effect transistor measurements and computational calculations. The observed charge transport properties are discussed in terms of the structural and electronic trends both within the series and in the context of the two more established analogue series, namely the bis(3-thiosemicarbazonato) and the diacetyl bis(3-thiosemicarbazonato) metal complexes. The Ni(II) analogues of the acenaphthenequinone bis(thiosemicarbazonato) family were found to exhibit p-type charge transport with mobilities between 10¯9 and 10¯5 cm2V¯1s¯1 depending on the exocyclic substitutent and resulting packing pattern. The observed results were rationalised in terms of the reorganisation energy and the charge transfer integrals. A series of 4,4`-phenyl-substituted nickel dithiolene complexes was synthesised and characterised. Initially with the aim of investigating the effect of varying the para-substituent of the phenyl ring on the charge transport properties, these efforts were undermined by the poor processability of these molecules by both vapour and solution phase methods. As a result, n-type charge transport could be observed under ambient conditions only for the phenyl and 4-bromo-phenyl substituted analogues, but the device performance was extremely poor. Nonetheless, the calculated reorganisation energies, charge transfer integrals and predicted mobilities were encouraging and may prompt further work on these materials. An all-organic analogue series of 4,4`-(4-halogen-phenyl)-substituted tetrathiafulvalenes was also investigated. The hole transport materials displayed mobilities of between 10¯3 and 10¯7 cm2V¯1s¯1 for both solution and vapour processed devices, depending on the nature of the halogen. These results are discussed in terms of their molecular properties and the calculated charge transport parameters and put in context of the performance of the 4,4`-bis(phenyl)-substituted benchmark analogue. Interestingly, the obtained crystal structure of the bromo-substituted analogue showed the molecule to be in the cis conformation, an observation that is unprecedented for simple, 4-phenyl,5-hydrogen substituted tetrathiafulvalenes, and indicates that both conformers are initially formed. Finally, a series of 4,4`-(2-alkyl)thienyl substituted nickel dithiolene salts and tetrathiafulvalenes was synthesised and characterised. While the charge transport properties of the former were not further investigated due to the low solubility of the neutral species, the tetrathiafulvalenes were incorporated into FET devices via solution processing. All exhibited comparatively high conductivity at room temperature (1.6x10¯3S m¯1), exceeding that of their quarterthiophene analogues. This masked the observed gate effects but indicates potential applications as conducting or charge transfer materials. While the two resolved analogues displayed trans geometry in the single crystal structures, powder diffraction and preliminary DSC measurements indicate that the materials displayed at least one additional phase, which once again likely corresponded to the cis conformer.

Metal dithiolenes [M(S2C2R2)n] have been studied for decades because of their interesting chemical and spectroscopic properties, which are related to the unusual electronic properties of the dithiolene ligand. The ligand-based reactivity of metal bisdithiolenes [M(S2C2R2)2] toward alkenes has been proposed for use in alkene purification schemes. According to the proposal, compounds Ni(S2C2R2)2 (R=CF3,CN) react with simple alkenes to form stable S,S-interligand adducts and the alkene can be released from the adduct by reduction. We showed that Ni(S2C2(CF3)2)2 reacts with ethylene and 1-hexene to form, preferentially, S,S-intraligand adducts, which rapidly decompose to inactive metal-containing materials and dihydrodithiins. However, the product selectivity can be significantly modified so that stable S,S-interligand adducts are obtained as dominant products by adding [Ni(S2C2(CF3)2)2]- to Ni(S2C2(CF3)2)2/alkene reaction mixtures. Mechanistic implications are discussed. Next, the reactions of Pt(S2C2(CF3)2)2 with 2,3-dimethyl-1,3-butadiene are addressed. Prior to our report, only symmetry-allowed S,S-interligand adducts had been observed as products in the reactions between conjugated dienes and metal bisdithiolenes. We discovered a novel mode of diene binding, where two dienes bind to one dithiolene ligand of Pt(S2C2(CF3)2)2, in an C,S-intraligand fashion, forming a new chiral bisthioether ligand. From bisdithiolenes, the focus shifts to new mixed-ligand molybdenum trisdithiolenes [Mo(S2C2(CF3)2)2(S2C6H4) and Mo(S2C6H4)2(S2C2(CF3)2)]. These complexes rapidly and cleanly bind ethylene, in an S,S-intraligand fashion, as predicted by MO arguments. The resulting intraligand adducts are sufficiently stable to be characterized, in contrast to the nickel bisdithiolene case. The metal-chelated dihydrobenzodithiin, formed upon ethylene addition, can be substituted with a variety of donor ligands, allowing access to new types of molybdenum dithiolenes. We have recently extended these studies to catalytic reactions: Mo(S2C2(CF3)2)2(S2C6H4) was used as a catalyst to form dihydrobenzodithiins from (S2C6H4)2 and a variety of alkenes, in the first example of dithiolene-based reactivity being exploited for carbon-heteroatom bond-forming catalysis. Finally, the synthesis, characterization and redox reactivity of a new Fe2Ni bis-double-decker complex is described, demonstrating for the first time a sandwich complex of a metal bisdithiolene with both NiS2C2 rings in an η5 π-donating mode. For the radical cation, experimental and computation evidence indicates that the lone electron is delocalized over the entire molecule.

Metal dithiolenes [M(S2C2R2)n] have been studied for decades because of their interesting chemical and spectroscopic properties, which are related to the unusual electronic properties of the dithiolene ligand. The ligand-based reactivity of metal bisdithiolenes [M(S2C2R2)2] toward alkenes has been proposed for use in alkene purification schemes. According to the proposal, compounds Ni(S2C2R2)2 (R=CF3,CN) react with simple alkenes to form stable S,S-interligand adducts and the alkene can be released from the adduct by reduction. We showed that Ni(S2C2(CF3)2)2 reacts with ethylene and 1-hexene to form, preferentially, S,S-intraligand adducts, which rapidly decompose to inactive metal-containing materials and dihydrodithiins. However, the product selectivity can be significantly modified so that stable S,S-interligand adducts are obtained as dominant products by adding [Ni(S2C2(CF3)2)2]- to Ni(S2C2(CF3)2)2/alkene reaction mixtures. Mechanistic implications are discussed. Next, the reactions of Pt(S2C2(CF3)2)2 with 2,3-dimethyl-1,3-butadiene are addressed. Prior to our report, only symmetry-allowed S,S-interligand adducts had been observed as products in the reactions between conjugated dienes and metal bisdithiolenes. We discovered a novel mode of diene binding, where two dienes bind to one dithiolene ligand of Pt(S2C2(CF3)2)2, in an C,S-intraligand fashion, forming a new chiral bisthioether ligand. From bisdithiolenes, the focus shifts to new mixed-ligand molybdenum trisdithiolenes [Mo(S2C2(CF3)2)2(S2C6H4) and Mo(S2C6H4)2(S2C2(CF3)2)]. These complexes rapidly and cleanly bind ethylene, in an S,S-intraligand fashion, as predicted by MO arguments. The resulting intraligand adducts are sufficiently stable to be characterized, in contrast to the nickel bisdithiolene case. The metal-chelated dihydrobenzodithiin, formed upon ethylene addition, can be substituted with a variety of donor ligands, allowing access to new types of molybdenum dithiolenes. We have recently extended these studies to catalytic reactions: Mo(S2C2(CF3)2)2(S2C6H4) was used as a catalyst to form dihydrobenzodithiins from (S2C6H4)2 and a variety of alkenes, in the first example of dithiolene-based reactivity being exploited for carbon-heteroatom bond-forming catalysis. Finally, the synthesis, characterization and redox reactivity of a new Fe2Ni bis-double-decker complex is described, demonstrating for the first time a sandwich complex of a metal bisdithiolene with both NiS2C2 rings in an η5 π-donating mode. For the radical cation, experimental and computation evidence indicates that the lone electron is delocalized over the entire molecule.

Les enzymes à molybdène ou à tungstène sont présentes dans toutes les formes de vie. La plupart d’entre elles sont des oxotransférases ou des hydroxylases. Elles contiennent un ou deux cofacteurs à molybdoptérine Moco coordiné au centre métallique par une fonction dithiolène. Ce cofacteur est très instable et la synthèse de complexes biomimétiques est difficile. Dans cette thèse, une nouvelle stratégie de synthèse d’un ligand dithiolène (qpdt) analogue du cofacteur à molybdoptérine a été développée. Le complexe de molybdène (Bu4N)2[MoO(qpdt)2] correspondant a été synthétisé et caractérisé. Ce complexe unique a montré un fort potentiel pour la réduction des protons. La photoréduction des protons en milieu acide (pH = 4), en présence du complexe de molybdène, du photosensibilisateur Ru(bpy)32+ et d’un excès d’acide ascorbique, donne d’excellentes activités allant jusqu’à 500 TONs en 15 heures. Ce complexe a aussi montré une très grande stabilité en milieu organique-acqueux. De même, l’électroréduction des protons par ce complexe dans l’acétonitrile a mis en évidence une constante de vitesse remarquable de 1030 s-1 à un potentiel de 1.3 V (vs Ag/AgCl). Afin de valoriser ce ligand original, les complexes bisdithiolène de nickel (Et4N)[Ni(qpdt)2] et de cobalt (Et4N)2[Co(qpdt)2]2 ont été synthétisés et caractérisés. Des études préliminaires de ces complexes ont montré un potentiel pour la photoréduction et l’électroréduction des protons. L’ensemble de ces résultats ouvre de nouvelles perspectives pour le développement de catalyseurs pour la réduction des protons. De plus, la synthèse de ce premier complexe biomimétique devrait permettre de mieux comprendre la chimie de ces enzymes encore peu connues. / Enzymes containing molybdenum or tungsten within their active sites appear to be present in all form of life. Most of them are oxotransferase or hydroxylase. They contain one or two pyranopterin-dithiolene cofactor, also called Moco, in which the metal is coordinated by the dithiolene moiety. The molybdenum cofactor is highly unstable and mimicking the active site of these enzymes is challenging. A new strategy for the synthesis of a pyranopyrazine dithiolene ligand (qpdt) has been developed in our laboratory. The corresponding molybdenum complex (Bu4N)2[MoO(qpdt)2] was synthesized and characterized extensively. This unique Mo-enzyme biomimetic complex demonstrated its potential for H2 production. This complex was shown to be active for the photoreduction of protons in acidic conditions (pH = 4), in the presence of the catalyst, the photosensitizer Ru(bpy)32+, ascorbic acid in exces and gave excellent activities of 500 TON with a high stability in aqueous organic media. Moreover, the electroreduction of protons by this complex in acetonitrile showed a remarkable rate constant value of 1030 s-1 at 1.3 V. (vs Ag/AgCl). To valorize this very original ligand qpdt, (Et4N)[Ni(qpdt)2] and (Et4N)2[Co(qpdt)2]2 bisdithiolene complexes were synthesized and characterized. Preliminary studies of theses complexes have shown a potential for the photoreduction and the electroreduction of protons. These results open new directions for the search of proton reduction catalysts. This first biomimetic complex should also be exploited to understand the chemistry of this class of oxidoreductase that is still not well understood.

archives@tulane.edu / This dissertation is dedicated to the study of the synthesis, crystal structures, properties, and reactivity of heteroleptic metallodithiolene complexes of the Group 10 metals. In this work, we report a systematic survey of the reactivity of [(Ph2C2S2)2M] (M = Ni, Pd, Pt) toward ligand substitution. The upshots of the survey are the clarification of the attributes of the incoming ligand that facilitate ligand displacement, creation of a new set of heteroleptic dithiolene complexes, [M(Ph2C2S2)(C≡NR)2] (M = Ni, Pd, Pt; R = Me, Bn, Cy, tBu, 1-Adamantyl, Ph), and improvement in the efficiency by which mixed-ligand “push-pull” compounds are made. The scope of dithiolene ligand displacement by incoming ligands was expanded beyond the already reported phosphine and diimine ligands. Spectroscopic and physical characterization techniques including S K-edge X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) were used in conjunction with DFT computational methods to establish the properties of the compounds prepared in this study. Representative [(Ph2C2S2)Pt(C≡NR)2] (R = aryl) complexes exihibited low temperature luminscence in frozen solvent glasses with relatively long lifetimes. The relevance of the dithiolene redox non-innocence in the ligand substitution mechanism has also been elucidated, thereby giving an insight into the fate of the displaced dithiolene ligand. Redox disproportionation between two radical monoanionic dithiolene ligands leads to the creation of a dithione, which is an enhanced leaving group and an inherently reactive species. When displacement of dithiolene ligand from [(Ph2C2S2)2Ni] was conducted with a twofold excess of C≡NCy, 4,5-diphenyl-1,3-dithiol-2-cyclohexylimine could be isolated. The identification and characterization of this compound is consistent with the creation of dithiobenzil during the ligand substitution. The reactive α-dithione is also capable of undergoing rapid irreversible polymerization, thereby providing the thermodynamic impetus for the dithiolene ligand substitution. Chemical oxidation of [Pt(Ph2C2S2)(C≡NtBu)2] with [N(C6H4Br-4)3][SbCl6] was undertaken to form [Pt(Ph2C2SˉS‧)(C≡NtBu)2]2[SbCl6]2. Structural determination of the dication revealed appreciable shortening and lengthening of C─S and C─C bond distances, respectively, within the dithiolene ligand as compared to the charge-neutral complex, an observation which confirmed the dithiolene ligand as the locus of the redox activity in the heteroleptic monodithiolene complexes. The utility of [M(Ph2C2S2)(C≡NMe)2] (M= Ni, Pd, Pt) as synthons in their own right for heteroleptic compounds not directly attainable by ligand substitution from [M(Ph2C2S2)2] was also explored. The panorama of outcomes when [M(S2C2Ph2)(CNMe)2] (M = Ni2+, Pd2+, Pt2+) are introduced to new ligands intended to substitute for CNMe has been thoroughly defined. The most significant breakthrough was the isolation of the dicyanide complex, [Et4N]2[Ni(S2C2Ph2)(C≡N)2], which is a potentially useful precursor toward cyanide-bridged multimetallic architectures. Finally, the synthesis and structural characterization of multimetallic complexes bridged by bis(diphenylphosphine) ligands and redox active dithiolenes as end capping ligands are described. The electrochemistry study revealed that the dimetallic compounds support reversible oxidation to dications, which likely have singlet diradical - triplet states in close equilibrium. The use of dithiolene ligands as electron spin hosts offers new possibilities for the application of metallodithiolene complexes in molecule-based spintronic devices, such as quantum bits (qubits). / 1 / Antony Obanda

Cette thèse est consacrée à la synthèse de complexes 3d homo et hétérométalliques avec des ligands bases de Schiff ou dérivés de la 1,2,4,5-tétrazine, à l’investigation de leur structure et de leurs propriétés physico-chimiques. Ce travail peut être divisé en trois parties. Dans la première partie, nous nous sommes principalement concentrés sur les ligands bases de Schiff, dérivés du salicylaldéhyde et des aminoalcools, formés in situ. Treize complexes hétérométalliques ont été obtenus et entièrement caractérisés. Il a été montré que les composés synthétisés possèdent une activité catalytique dans la réaction de l’oxydation photochimique de l’eau, présentent des propriétés de photoconductive dans les polymères composites et peuvent être utilisés pour le développement de matériaux multifonctionnels. La deuxième partie décrit la fonctionnalisation des ligands base de Schiff par l’introduction dans leur structure des unités tétrathiafulvalène et métaux dithiolènes électroactives. Deux nouvelles familles de ligands ont été synthétisées et caractérisées. La série de sels de radicaux cations et de complexes dithiolènes homo et hétérométalliques ainsi que leurs propriétés physiques ont été discutées. La dernière partie est consacrée aux ligands à base de tétrazine. Les principaux avantages du noyau tétrazine ont été discutés. Deux nouveaux ligands dérivés de la picolylamine et leurs complexes 3d mono- et binucléaires ont été décrits. / The thesis is devoted to the synthesis of homo- and heterometallic 3d-metal complexes with Schiff base ligands or derivatives of 1,2,4,5- tetrazine, together with the investigation of their structural and physico-chemical properties. This work can be divided in three parts. In the first part we have been mainly focused on the Schiff base ligands, derivatives of the salicylaldehyde and aminoalcohols. Thirteen heterometallic complexes were obtained and fully characterized. It has been shown that the synthesized compounds possess catalytic activity in the photochemical water oxidation, exhibit photoconducting properties in polymeric composites and can be used for the development of multifunctional materials of wide use. The second part describes the functionalization of Schiff base ligands by the introduction into their structure of electroactive tetrathiafulvalene and dithiolate moieties. Two new families of ligands were synthesized and characterized. The series of radicalcation salts and homo- and heterometallic dithiolene complexes together with the investigation of their physical properties have been described. The last part is devoted to the tetrazine based ligands. The main advantages of the tetrazine ring have been discussed. Two new ligands, derivative of picolylamine and their mono- and binuclear 3d-metal complexes are reported. In conclusion, perspectives of further research related to the described results were highlighted.

Polyimide membranes containing nickel dithiolenes were investigated for the separation of propylene and propane. Permeation and sorption experiments were conducted as well thermal property analyses. Results indicate that the dithiolene has an antiplasticizing effect on the polymers studied. Upon addition of the dithiolene there is a subsequent reduction in the permeability coefficient and the permeability selectivity remains relatively unchanged. There is some evidence of increases in solubility selectivity, but a larger decrease in diffusivity selectivity results in a decrease in the permeability selectivity. Investigation of the thermal and mechanical properties of dithiolene-containing films indicates a reduction in fractional free volume as well as the glass transition temperature when compared to the pure polymer. There is also an increase in the modulus of the films upon addition of the dithiolene. The implications of these results and their correlation with antiplasticization are discussed.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23721号 / 理博第4811号 / 新制||理||1689(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM