New Bimetallic Monovalent Aluminium and Gallium Systems with Alkali Metals and Rhodium for Small Molecule and C–H Activation
Over the past decade, synthetic chemistry has seen groundbreaking advances stemming from the design of low-valent main-group compounds. In particular, monovalent Group 13 metals, most notably aluminium(I) and gallium(I), have garnered attention for their carbene-like behaviour, which facilitates tra...
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| Tipo de recurso: | tesis doctoral |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Universidad de Huelva (UHU) |
| Repositorio: | Arias Montano. Repositorio Institucional de la Universidad de Huelva |
| Idioma: | inglés |
| OAI Identifier: | oai:ariasmontano.uhu.es:10272/27186 |
| Acceso en línea: | https://hdl.handle.net/10272/27186 |
| Access Level: | acceso abierto |
| Palabra clave: | Aluminium Galium Rhodium Cooperativity Bimetallic systems Aluminio Galio Rodio Cooperatividad Sistemas bimetálicos 2303.21 Compuestos Organometálicos 2303.07 Compuestos de Coordinación 2210.01 Catálisis 2303.03 Elementos Alcalinos 2303.02 Elementos Alcalinotérreos 2303.29 Elementos de Transición 2303.14 Hidrogeno |
| Sumario: | Over the past decade, synthetic chemistry has seen groundbreaking advances stemming from the design of low-valent main-group compounds. In particular, monovalent Group 13 metals, most notably aluminium(I) and gallium(I), have garnered attention for their carbene-like behaviour, which facilitates transformations once believed to be the exclusive domain of transition metals. By broadening the core concepts of main-group reactivity, these electron-rich Al(I) and Ga(I) species have demonstrated the capacity to break strong bonds (e.g., H–H, C–H, C–C) and to mediate catalytic processes. Their success underscores a dramatic shift in modern chemistry, where main-group elements can mirror or even rival classical transition-metal reactivities through clever ligand architectures and metal–metal cooperative effects. This Doctoral Dissertation centres on synthesising, characterising, and harnessing the reactivity of new Al(I) and Ga(I) complexes featuring a variety of metal–metal bonding interactions. A systematic approach is adopted to elucidate both their solid-state structures, with a focus on how these frameworks promote electron sharing or donation, and their solution-phase equilibria, which reveal fluxional behaviours and dynamic aggregation. Through subtle changes such as tuning the alkali-metal cations or coupling to transition metals, we uncover novel pathways for challenging bond activations. The Thesis is organised into three interlinked Chapters, each spotlighting a particular facet of these low-valent species, spanning aggregation modes with different alkali metals to cooperative interactions with transition metals (notably rhodium). Special emphasis is placed on activating inert substrates, such as dihydrogen (H2), and exploring the pursuit of C–H bond activation under mild conditions, thereby drawing parallels to and extending beyond the capabilities of typical d-block catalysts. Collectively, this Thesis highlight how such low-valent main-group metal platforms, stabilised by an intricate network of metal–metal bonding, can mimic, complement, or even surpass conventional transition-metal reactivity. By integrating experimental insights with computational models, this work paints a comprehensive picture of how Al(I) and Ga(I) carbene surrogates, in concert with carefully chosen counterions or transition-metal centres, represent a frontier in small-molecule activation and selective catalytic transformation. ------------------------------------------------------------------------------------------------- |
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