The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Isotope shift studies in the rare earths and lead

Isotope shifts of K_α1 x-ray transitions were measured for the Neodymium isotopes Nd 142, 143, 144, 145, 146, 148 and 150, the Samarium isotopes Sm 147, 148, 149, 150, 152 and 154, the Gadolinium isotopes Gd 154, 155, 156, 157, 158 and 160, the Dysprosium isotopes Dy 162 and 164, the Erbium isotopes Er 166, 168 and 170, the Hafnium isotopes Hf 178 and 180 and the Lead isotopes Pb 204, 206, 207 and 208. A curved crystal Cauchois spectrometer was used. The analysis of the measurement furnished the variation of the mean square charge radius of the nucleus, δ˂r²˃, for 23 isotope pairs. The experimental results were compared with theoretical values from nuclear models. Combining the x-ray shifts and the optical shifts in Nd and Sm yielded the optical mass shifts. An anomaly was observed in the odd-even shifts when the optical and the x-ray shifts were plotted against each other.

Mujeres y Derecho: pasado y presente. I Congreso Multidisciplinar de Centro - Sección de Bizkaia de la Facultad de Derecho

Cuando se aborda el estudio de la teoría del estado o del derecho se investiga desde una perspectiva androcéntrica, fruto del sistema patriarcal en el que estamos inmersas e inmersos investigadoras e investigadores, de manera que se obvia la presencia o ausencia de las mujeres en el ámbito de estudio del que se trate. Y el estudio de la historia de las mujeres es necesario para cualquier investigación que pretenda referirse a la humanidad entera. Hay muchos trabajos que abordan el estudio de las materias que aquí se tratan, pero ninguno de ellos se ocupa de manera sistemática o detallada de la participación de las mujeres en ese momento histórico o en la elaboración de los conceptos que sirven de base a nuestros actuales estados constitucionales.

Analysis on a new type magneto-optical disk for blue lasers

The conventional TbFeCo magneto-optical (MO) medium has a relatively smaller Kerr rotation angle in the blue region than in the red. With the recording wavelength gradually moving to the short wavelength, if TbFeCo is still used as recording medium, the conventional MO disk structure must be optimized to get a larger carrier to noise ratio (CNR). Sabi et al. have found that adding a metal layer attached to the TbFeCo film as thermal control layer is a useful way to get a high CNR. In this paper, we proved this through calculation, and carried out optimization of the new type of disk. Calculation results showed that the new structure is useful in preventing an excessive temperature increase, and has a better thermal response. (c) 2005 Elsevier B.V. All rights reserved.

输出5W的电光调Q Nd：YAG陶瓷激光器

研究了激光二极管（LD）侧向抽运的Nd：YAG陶瓷电光调Q激光器的激光输出特性。该激光器采用九组激光二极管线阵列（LDA）侧面紧密环绕均匀排布的抽运结构，并用微通道热汇冷却技术冷却。在电光调Q方式下，重复频率为100Hz，抽运单脉冲能量为416mJ时，用尺寸为庐5mm×75mm，掺杂原子数分数为1％的Nd：YAG陶瓷棒，获得50mJ的1064nm激光输出，脉冲宽度为12ns，斜率效率达24％。并实验测量和分析了偏振片，KD^＊P晶体，四分之一波片等调Q器件的插入损耗。测量了输出激光时间波形和光斑的光强空间

LD抽运的Nd：YLF／Cr^4＋：YAG被动调Q激光器

报道了激光二极管（LD）抽运的Nd：YLF激光器，采用平凹腔结构，分别用两片Cr^4＋：YAG可饱和吸收晶体，实现了被动调Q，输出激光波长为1053nm。采用厚度为0．5mm小信号透过率为90％的Cr^4＋ YAG，在泵浦功率最大为17W时，输出脉冲宽度为60．6ns，平均功率为1．5W，重复频率为9．5kHz，单脉冲能量为157．9mJ；采用厚度为0．55mm小信号透过率为95％的Cr^4＋ YAG，在泵浦功率最大为17W时，输出脉冲宽度为68．6ns，平均功率为1．35W，重复频率为14kHz，单脉冲

双包层光纤侧面耦合器

研究了一种侧面抽运双包层光纤的方法，从被剥除了外包层、端面为350μm×400μm的D型双包层光纤内包层上切下长度为3mm的一段柱体，并胶合在相同的双包层光纤内包层的侧面上，构成了柱体-光纤侧面耦合器。半导体激光器的抽运光从该柱体的一端入射并通过它耦合进入双包层光纤的内包层，实验测得耦合器最大耦合效率为85％。该方法适用于输出功率为数瓦的光纤激光器和放大器的侧面抽运。