This thesis presents the synthesis, characterization and reactivity of a series of palladium complexes that contain redox-active verdazyl ligands. This work was motivated by the possibility of discovering new and interesting reactivity that may eventually lead to the development of new chemical reactions. A bidentate verdazyl radical ligand that contains an aryl phosphine was synthesized. Reaction of this ligand with (PhCN)2PdCl2 yielded a square planar (verdazyl)PdCl2 complex. Structural and spectroscopic data suggest that this compound consists of a ligand-centered radical coordinated to a Pd(II) center. The radical complex was chemically reduced by one-electron to generate a binuclear chloride-bridged [(verdazyl)PdCl]2 complex. In this reduced complex, both metals were still Pd(II) and the verdazyl ligand was determined to be in its singly reduced, monoanionic charge state. The original radical PdCl2 complex could be regenerated via one-electron oxidation of the reduced complex using PhICl2. The verdazyl ligands in the reduced complex could also be reversibly protonated to generate “leuco” verdazyl complex (verdazyl-H)PdCl2. Reaction of the radical (verdazyl)PdCl2 complex with water triggers a ligand-centered redox disproportionation reaction. A series of bis(verdazyl) palladium complexes were synthesized using a bidentate pyridine-substituted verdazyl ligand. Reaction of two equivalents of radical ligand with (CH3CN)4Pd2+ yielded a (verdazyl)2Pd(solvent)2+ complex (solvent = CH3CN or DMSO). In this complex, one verdazyl radical ligand chelates to palladium and the other binds as a monodentate ligand. Two-electron reduction of this complex generated a (verdazyl)2Pd complex in which two monoanionic verdazyl ligands are bound to a central Pd(II) ion. This reduced complex could also be made via reaction of 0.5 equivalents of Pd(0)2(dba)3 with two equivalents of radical ligand. In this reaction, the metal is oxidized by two electrons and each ligand is reduced by a single electron. Two-electron oxidation of the reduced complex in the presence of DMSO yielded the original bis(radical)complex, (verdazyl)2Pd(DMSO)2+. Chlorination of the reduced complex using one equivalent of PhICl2 (two-electron oxidation) resulted in dissociation of one verdazyl ligand to afford a 1:1 mixture of free verdazyl : (verdazyl)PdCl2, in which both of the verdazyls are neutral radicals. Reaction of the reduced complex with 0.5 equivalents of PhICl2 (one-electron oxidation) yielded a (verdazyl)2PdCl complex that contained a bidentate reduced verdazyl ligand and a monodentate radical ligand. All three of the oxidation reactions described above adhere to ligand-centered redox chemistry. Reaction of the reduced (verdazyl)2Pd complex with excess HCl resulted in protonation of both the anionic verdazyl ring and the pyridyl group to generate a leuco/pyridinium tetrachloropalladate salt, (verdazyl-H2)2(PdCl4). The protonated salt could be converted back to the original (verdazyl)2Pd complex by deprotonation with water. Palladium complexes of a tridentate NNN-chelating verdazyl ligand were prepared and their redox chemistry was explored. Reaction of the radical ligand with (CH3CN)4Pd2+ yielded radical complex (verdazyl)Pd(NCCH3)2+. The tridentate ligand was also prepared in its reduced, leuco form (verdazyl-H). Reaction of the leuco verdazyl with (CH3CN)2PdCl2 generated HCl and a (verdazyl)PdCl complex in which the ligand is in its monoanionic charge state. The reduced (verdazyl)PdCl complex was reacted with AgBF4 to afford (verdazyl)Pd(NCCH3)+ via chloride abstraction; the verdazyl remained in its reduced charge state following the reaction. Both reduced complexes (chloro and acetonitrile) were oxidized by a single electron to afford the corresponding radical complexes. These radical complexes could be reduced by a single electron to regenerate the original reduced complexes. Like the previous two projects, all of the redox chemistry was ligand-centered. The reactivity of these complexes with primary amines was also explored. Reaction of radical complex (verdazyl)Pd(NCCH3)2+ with n-butylamine resulted in one-electron reduction of the verdazyl ligand. We were unable to determine the mechanism of the reaction, but the reactivity that was observed demonstrates the potential for verdazyl-palladium complexes to be used in the design of new radical reactions. / Graduate / 2018-07-17

Abstract: Pincer compounds are organometallic complexes with intriguing tunable reactivities. In this work we explore their unique properties and reactivities through spectroscopic and computational investigations, with a focus on the PN3P pincer platform. First, we conducted a computational study on five pincer complexes with stereogenic phosphine arms that have multiple well-defined rotamers. Significant energy differences could be found between the lowest and highest energy rotamer in each set of pincer complexes. All rotamers for reactant, transition state, and product, were evaluated in a reaction energy profile of a CO2 reduction by a pincer nickel hydride, and we found that this reaction could be found either favorable or unfavorable, depending on the choice of rotamer. A software to generate rotamers has been developed and applied to the work presented in this part. The zwitterionic aromatic resonance form has a large contribution in the dearomatized PN3P* nickel pincer complexes, which is demonstrated by the imine arm's ability to act as an organic σ-donor, similar to NHC catalysts. Related to this property, as well as the pincer compound's ability to undergo metal-ligand cooperation catalysis, is the basicity (or acidity) of pincer ligand spacer arms. Therefore, we have determined the Brønsted basicity of the imine arm in three PN3P* nickel pincer complexes in THF. The relative basicity was found to be strongly influenced by the X ligand trans to the PN3P* ligand, and less by alkyl groups on phosphine donor arms. Finally, we explored the reactivity between a PN3P* rhodium carbonyl pincer complex and dioxygen at room temperature in solution, and at elevated temperature in the solid state. Intriguingly, the singlet PN3P* rhodium carbonyl complex reacts with the triplet dioxygen both in solution and in the solid state to afford oxidation on the ligand backbone. This is possible due to the ligands ability to do a single-electron transfer to dioxygen. The solid state reaction was studied with in situ rhodium K-edge X-ray absorption spectroscopy under dioxygen flow, where an isobestic point was observed, and simulation studies support formation of a Rh-O2 adduct. In situ FTIR studies in a static dioxygen environment revealed that the PN3P* rhodium carbonyl complex is able to facilitate the incorporation of O2 into CO and CO2.

Redox-active ligands deliver redox equivalents to impart multi-electron functionality at 3d metals that typically undergo to one electron redox events. It was proposed that 3d metals with redox-active ligands could form unusually well-defined catalysts for C-C bond forming reactions to mimic palladium-type reactivity. Therefore, several new complexes containing an iron or cobalt with redox-active ligands were synthesized and tested for their ability to form new C-C bonds. A bis(iminosemiquinone) iron (III) complex was able to homocouple aryl Grignards using dioxygen as the terminal oxidant. However, ligand redistribution prevented detailed mechanistic study of the C-C bond forming reaction and led to catalyst degradation. To address the challenges seen in the iron catalyst a new cobalt electron transfer (ET) series containing a pincer-type bis(phenolate) N-heterocyclic carbene ligand (CoNHC) was synthesized. Studies indicate the CoNHC ET series spans multiple-electrons by corporative metal and ligand redox. These complexes were evaluated for cross-coupling of alkyl halides and aryl Grignards. Mechanistic studies imply that the low cross-coupling yields were due to ligand degradation. However, CoNHC catalytically activate cross-couples ether nitriles and aryl Grignards via a novel C-O bond activation leading to a new C-C bond. Findings concerning redox-active ligands on iron and cobalt for C-C bond forming reactions and implications for future research are discussed.

In this study, we describe a detailed investigation of cobalt complexes containing redox-active ligands. We have prepared an electronic series of the complex in three oxidation states: [CoIII(ap)2]-, CoIII(isq)(ap), and [CoIII(CH3CN)(isq)2]+. Characterization shows that the metal center remains cobalt(III) through the redox changes and indicates that the oxidation state changes occur with gain or loss of electrons from the ligand set. While CoIII(isq)(ap) reacts with halide radicals to form a new cobalt-halide bond in a single electron reaction, [CoIII(ap)2]- appears to be prone to multi-electron reactivity in reactions with sources of "Cl+". Both reactions occur with electrons derived from the ligand set. Mechanistic studies suggest a single, two electron step is responsible for the bond-formation. Similarly, [CoIII(ap)2]- reacts with alkyl halides to pseudo-oxidatively add the alkyl at the cobalt center. The product of the reaction can be isolated and fully characterized and was found to be best assigned as CoIII(alkyl)(isq)2. This assignment indicates that the reaction occurs, again, with the new bond formed with two electrons formally derived from the ligand set and with no change in oxidation state at the metal center. Mechanistic investigations of the pseudo-oxidative addition suggest the reaction is SN2-like. The reaction occurs with a wide scope of alkyl halides, including those containing beta-hydrogens. The cross-coupling reaction of CoIII(alkyl)(isq)2 with RZnX forms a new carbon-carbon bond. Similarly, the two electron oxidized complex [CoIII(CH3CN)(isq)2]+ reacts with organozinc reagents to couple two carbon nucleophiles and form a new carbon-carbon bond. Both reactions are successful with both sp2 and sp3 carbons. When followed substoichiometrically, the homocoupling reaction can be observed to form CoIII(alkyl)(isq)2. This indicates that the homocoupling and cross-coupling reactions proceed by the same mechanism. However, both reactions have low yields. The yield of the reactions are decreased by steric bulk of the alkyl or aryl fragments or around the metal center created by substituents on the ligand. Also, while the steric congestion disfavors the addition of the first alkyl fragment, the addition of the second alkyl fragment and subsequent rapid elimination of the coupling product is almost completely inhibited. This result also implies that the coupling of the two alkyl fragments is entirely inner-sphere requiring installation of both for coupling. In a complementary study, use of bidentate or tridentate stabilizing ligands in combination with one redox-active catechol-derived or amidophenol-derived ligand was investigated. With the synthesis of (triphos)CoII(cat) and the one electron oxidized [(triphos)CoII(sq)]+, it is evident that the oxidation occurs at the ligand and not the metal. Reaction of (triphos)CoII(cat) with a Cl+ reagent generated a new material which we tentatively describe as (triphos)CoIII(Cl)(sq). This implies that the two electrons used to create the new cobalt-halide bond are derived from both the ligand and the metal, one from each. We believe the complex is unreactive with organic halides due to the steric bulk surrounding the metal center. Similar cobalt complexes containing tridentate or bidentate phosphine ligands or a tridentate pyrazol ligand in combination with a catechol-derived or amidophenol-derived ligand resulted in unsuccessful synthesis or unstable complexes. Throughout the course of both of these studies, steric crowding at the metal center is a problem disfavoring the facilitated reactivity. We have however shown that the amidophenol ligands have favorable molecular orbital overlap with the cobalt to act as an electron reservoir and facilitate reactivity at the metal center. We have also shown that this combination can create a proclivity to facilitate multi-electron reactions at the metal that is naturally prone to radical reactions.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24177号 / 理博第4868号 / 新制||理||1697(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 有賀 哲也, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

<div><div><div><p>The chemistry of the f-block is relatively unknown when compared to the rest of the periodic table. Transition metals and main group elements have enjoyed thorough study and development over the last 200 years, while many of the lanthanides and actinides weren’t even discovered until the 1940’s. This is troublesome, as knowledge of these elements is critical for environmental, industrial and technological advances. Understanding bonding motifs and reactivity pathways is fundamental to advancing the field of f-block chemistry. The use of redox- active ligands has aided in the construction of new bonding modes and discovery of new reaction pathways by providing electrons for these transformations. A particularly successful partnership is formed when redox-active ligands are combined with lanthanides, as these elements are usually considered redox-restricted. A series of lanthanide complexes featuring the iminoquinone ligand in three oxidation states will be discussed. The use of the ligands as a source of electrons for reactivity is also described, with new bonding motifs for lanthanides being realized. The iminoquinone ligand can also serve to break bonds. The uranyl (UO22+) ion is notoriously difficult to handle due to its strong U-O multiple bonds. To overcome this, we developed a series of uranyl complexes and studied the ability of the iminoquinone ligand to serve as an electron source for reduction of uranium, with concomitant U-O bond cleavage.</p></div></div></div>

La capacité des complexes de lanthanides divalents à promouvoir des réductions inhabituelles suscite actuellement un grand intérêt, tout particulièrement leur aptitude à activer des petites molécules telles CO2 et N2 dans des conditions douces. Les ions lanthanides, de par leurs propriétés de coordination tout à fait uniques pourraient offrir une alternative aux métaux de transition couramment utilisés pour la conception de catalyseurs. Cependant, comparativement aux métaux du bloc d, la chimie de coordination des lanthanides est exclusivement dominée par des transferts mono-électroniques qui impliquent uniquement les capacités rédox du centre lanthanide. C'est pourquoi le développement de nouveaux complexes de lanthanides capables de réaliser des réductions poly-électroniques est particulièrement intéressant. Dans un premier temps, nous avons utilisé des ligands rédox-actifs de type base de Schiff π-conjuguées pour étudier la chimie des ions lanthanides en réduction. Cela nous a permis d'isoler des complexes dans lesquels deux ou quatre électrons sont stockés sur le ligand via la formation de liaisons C-C. Ces mêmes liaisons sont rompues en présence d'agents oxydants et les électrons sont libérés pour réaliser des transformations multi-électroniques. Ce procédé a été observé pour des bases de Schiff tridentates et tétradentates, ce qui nous a permis de moduler les propriétés rédox des composés. La réactivité avec CO2 des complexes synthétisés a également été étudiée et nous avons identifié des complexes de néodyme capables de réduire le CO2. Dans un second temps, nous nous sommes intéressés à l'étude de complexes de cobalt contenant des ligands rédox-actifs de type base de Schiff π-conjuguées capables de stocker des électrons sous forme de liaisons C-C. Ce système, déjà étudié dans les années 1990, avait démontré sa capacité à activer le CO2. Avec l'intention de déterminer l'espèce active dans la réaction avec CO2, nous avons revisité ce système et mis en lumière un équilibre d'isomérie rédox entre un complexe de Co(I) et un complexe de Co(II) où un électron peut être localisé sur le métal ou sur le ligand. Nous nous sommes également intéressés aux paramètres qui régissent cet équilibre. En particulier, nous avons étudié l'influence de l'architecture du ligand sur les propriétés rédox des complexes de cobalt. Ces études offrent de nouvelles perspectives pour le développement de complexes capables d'effectuer la réduction électrocatalytique du CO2. / The redox chemistry of lanthanide complexes is attracting increasing interest because of the potential of divalent lanthanide complexes to promote unusual redox chemistry. For example they are able to activate small molecules such as CO2 and N2 in mild conditions. Due to the unique coordination and bonding properties of the lanthanide ions, their compounds could provide an attractive alternative to transition metals for the catalytic transformation of small molecules. However, metal-based multi-electron processes remain uncommon in lanthanide chemistry especially in comparison with the d-block metals; the chemistry of low-valent lanthanides being dominated by single-electron transfers. In this context, the first aim of this project was to investigate the association of lanthanides with a redox-active ligand acting as an independent electron reservoir within the same molecule. Accordingly, we examined the use of highly π-delocalized Schiff base ligands to study the reductive chemistry of lanthanide ions. This led to the isolation of electron-rich complexes which are stabilized by storing two or four electrons on the ligands through the formation of C-C bonds. Interestingly, these C-C bonds can be cleaved by oxidizing agents and the electrons released can participate in multi-electron redox reactions. This process was observed within different tridentate and tetradentate Schiff-base ligand scaffolds, allowing a tuning of the properties of the compounds. The ability of these complexes to react with CO2 has been studied, which lead to the identification of some neodymium complexes capable of reducing CO2. The second part of this work was dedicated to the study of cobalt complexes bearing redox-active and highly π-delocalized Schiff base ligands able to store electrons through the formation of C-C bonds. Seminal studies on Schiff base complexes of cobalt had been carried out in the 1990's and they demonstrated the ability of these complexes to activate CO2. With the aim to identify the active species responsible for CO2 activation, we have revisited these systems and highlighted a redox-isomeric equilibrium between a Co(I) and a Co(II) complexes where the electron can be localized on the cobalt or on the ligand. We also investigated the parameters influencing this equilibrium. In particular we have investigated the effect of the ligand architecture on the redox reactivity of cobalt complexes. Such studies pave the way to the development of new complexes for the electrocatlytic reduction of CO2.

Ce travail de thèse portait sur la synthèse et l'étude de complexes magnétiques redox-actifs comme prototypes pour la conception d'aimants moléculaires à haute température. L'activité redox est assurée par le ligand pontant, qui peut moduler et parfois améliorer significativement les propriétés magnétiques. Après un chapitre d'introduction présentant les derniers développements dans le domaine des matériaux magnétiques moléculaires, un accent particulier est mis sur l'importance d'avoir un fort couplage d'échange magnétique J entre les porteurs de spin. Une étude bibliographique présentant deux approches émergentes pour augmenter J dans les composés polynucléaires est également présentée et discutée. Le chapitre 2 présente les synthèses et caractérisations de complexes dinucléaires [M2(tphz)(tpy)2](PF6)n (M = Co(II) ou Ni(II); n = 4, 3, 2, tphz = tétrapyridophénazine, tpy = terpyridine) construits à partir de ligands pontant (tphz) et bloquant (tpy) fortement coordinants et redox-actifs. Les études approfondies de ces composés montrent que le ligand pontant redox-actif peut être utilisé comme un outil de choix pour promouvoir une délocalisation des spins, de forts couplages magnétiques, ainsi que de la commutabilité. L’analyse des résultats obtenus permet également de mieux comprendre les paramètres clés pour l’élaboration de systèmes fortement couplés magnétiquement. Dans le prolongement de ce travail visant à sélectionner les meilleurs composants pour la conception rationnelle d'aimants moléculaires à haute température, le chapitre 3 décrit une nouvelle série de complexes mononucléaires [Cr(III)(tphz)(tpy)](CF3SO3)n (n = 3, 2, 1). Les complexes mono- et doublement réduits présentent des interactions magnétiques remarquablement fortes entre les ions métalliques et les ligands radicalaires, et pourraient servir d'unités magnétiques intéressantes pour la conception d'aimants de plus hautes nucléarités. / The thesis work aims at the synthesis and study of redox-active magnetic molecules as prototypes towards the design of molecule-based magnets with high operating temperature, a prerequisite for technological applications. The redox activity is provided by the bridging ligand, which could tune and sometimes enhance significantly the magnetic properties of the resulting molecular architectures. After an introduction chapter presenting the latest developments in the field of molecule-based magnetic materials, special emphasis is given on the importance of having large magnetic exchange coupling J between the spin carriers to reach high operating temperature. This is supported by a bibliographic study concerning two emerging approach to enhance J values in polynuclear compounds. Chapter 2 presents the syntheses and characterizations of dinuclear M(II) complexes [M2(tphz)(tpy)2](PF6)n (M = Co or Ni; n = 4, 3, 2, tphz = tetrapyridophenazine) built by using strongly complexing, redox-active bridging ligand (tphz), and terpyridine (tpy) as capping ligands. The extensive studies on these compounds show that the redox-active bridging ligand can be used as a tool to promote spin delocalization, high spin complexes and magnetic multi-switchability. Importantly the work reveals the key parameters towards building strongly magnetically coupled systems. As a continuation research of finding the best magnetic components for the rational design of high temperature molecule-based magnets, Chapter 3 describes a new series of [Cr(III)(tphz)(tpy)](CF3SO3)n (n = 3, 2, 1) mononuclear complexes. Both the mono and doubly-reduced complexes show remarkable magnetic interactions between metal center and radical ligands, which could further act as interesting magnetic units for the design of higher nuclearities magnets.

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