Reactivity of dinitrogen and hydrocarbons for C–N bond formation

Project Information

READHY

Grant agreement ID: 101109769

DOI

10.3030/101109769

EC signature date 10 August 2023

Start date 1 February 2024

End date 31 January 2027

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 261 380,64

Coordinated by

UNIVERSIDAD DE SEVILLA
Spain

Periodic Reporting for period 1 - READHY (Reactivity of dinitrogen and hydrocarbons for C–N bond formation)

Reporting period: 2024-02-01 to 2026-01-31

Summary of the context and overall objectives of the project

The activation and functionalisation of dinitrogen (N2) remains one of the most important and long-standing challenges in chemistry. Despite being the most abundant form of nitrogen in the atmosphere, its strong triple bond renders it chemically inert, requiring energy-intensive industrial processes such as the Haber–Bosch process for its conversion into ammonia. While highly successful, this process is associated with significant energy consumption and environmental impact, accounting for a substantial fraction of global CO2 emissions.
In this context, the development of alternative strategies for the direct transformation of N2 into value-added chemical products under mild conditions represents a major scientific and technological goal. In particular, the formation of C–N bonds directly from dinitrogen and unactivated hydrocarbons would constitute a paradigm shift in synthetic chemistry, enabling more sustainable routes to nitrogen-containing organic molecules, which are essential in pharmaceuticals, agrochemicals, and advanced materials.
The READHY project is positioned within this global challenge and aims to contribute to the development of innovative catalytic systems capable of achieving this transformation. The project focuses on the design of iron-based catalysts supported by novel bifunctional diketiminate ligands, combining ligand engineering with advanced organometallic chemistry to promote N2 activation and subsequent functionalization.
The overall objective of the project is to establish new catalytic pathways for the formation of C–N bonds directly from dinitrogen and hydrocarbons. This is pursued through a multidisciplinary approach that integrates ligand design, synthesis of metal complexes, and mechanistic studies of bond activation processes. The project also explores alternative activation strategies, including the study of strong bond activation (such as C–H bonds) using related systems, providing complementary insights into reactivity and catalytic design.
The project pathway to impact is based on the generation of fundamental knowledge that can enable future technological developments. By advancing the understanding of N2 activation and reactivity, the project lays the groundwork for the design of more efficient and sustainable catalytic processes. Although the outcomes at this stage are primarily fundamental, their long-term implications are significant, as they may contribute to reducing the reliance on energy-intensive industrial processes and support the transition towards greener chemical technologies.
Within the broader European strategic context, the project aligns with key priorities related to sustainability, climate neutrality, and the development of environmentally friendly chemical processes. By targeting the efficient use of abundant resources such as atmospheric nitrogen and earth-abundant metals like iron, the project supports the objectives of reducing environmental impact and promoting resource-efficient technologies.
The expected impact of the project is therefore twofold: in the short term, it contributes to advancing fundamental scientific knowledge in organometallic chemistry and catalysis; in the long term, it has the potential to influence the development of sustainable nitrogen conversion technologies with wide-ranging applications.
Although the project is primarily rooted in chemistry, it also indirectly engages with broader societal and environmental challenges, particularly those related to energy consumption and sustainability. The development of alternative chemical processes with reduced environmental footprint contributes to addressing global challenges at the interface of science, technology, and society.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

During the reporting period, the project has focused on establishing the synthetic and conceptual framework required to enable the activation and functionalisation of dinitrogen. The work carried out has combined ligand design, synthesis of coordination compounds, and investigation of their reactivity towards strong bond activation.
A central activity has been the development of tailored ligand systems designed to control the electronic and steric properties of the metal centre. In this context, a family of ligand frameworks has been successfully synthesised, providing versatile platforms for coordination chemistry. These systems are structurally related to the original design and preserve key features relevant for reactivity studies.
The coordination of these ligands to different metal centres, including alkali metals, has enabled a systematic exploration of their chemical behaviour. In particular, the project has made significant progress in the study of C–H bond activation processes using these systems. A comparative approach involving different alkali metals (e.g. Na, K) has allowed the identification of clear trends in reactivity and highlighted the role of the metal in modulating bond activation.
These studies have demonstrated that the designed ligand environments can support the activation of strong chemical bonds under controlled conditions. The results provide valuable mechanistic insights into the reactivity of s-block metal systems and establish a strong foundation for further development.
In parallel, the work has contributed to a deeper understanding of the interplay between ligand structure, metal identity, and reactivity. This knowledge is essential for guiding the next stages of the project, particularly in the context of activating highly inert molecules such as dinitrogen.
Overall, the project has achieved important progress in building the chemical tools and conceptual understanding required to address its core objectives. The results obtained during this period provide a robust basis for the continuation of the research and the achievement of the project’s long-term goals.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The results obtained during the reporting period contribute to advancing the current state of the art in the field of small molecule activation and organometallic chemistry. In particular, the development of tailored ligand frameworks capable of supporting reactivity with earth-abundant metals represents a significant step forward in the design of sustainable catalytic systems.
The systematic investigation of C–H activation processes using alkali metal systems supported by these ligands provides new insights into the reactivity of s-block elements, an area that remains comparatively underexplored. The identification of clear trends in reactivity as a function of the metal highlights the potential of these systems to mediate challenging bond activation processes, traditionally dominated by transition metal chemistry.
Furthermore, the project has established a versatile ligand platform that can be adapted to different metals and reactivity contexts. This flexibility is particularly relevant for the future development of catalytic systems targeting the activation of highly inert molecules such as dinitrogen. The knowledge generated on structure–reactivity relationships constitutes a key advance beyond the current state of the art and provides a rational basis for the design of next-generation catalysts.
From an impact perspective, the results lay the foundation for the development of more sustainable chemical transformations based on abundant elements and mild conditions. In the longer term, this approach has the potential to contribute to reducing the environmental footprint of nitrogen-related chemical processes and to enable more efficient routes to nitrogen-containing organic compounds.
To ensure further uptake and maximise the impact of these results, several key needs can be identified:
• Further research: Continued investigation is required to translate the observed reactivity into catalytic processes, particularly in the context of dinitrogen activation and C–N bond formation.
• Methodological development: Optimisation of ligand design and reaction conditions will be essential to enhance stability, reactivity, and selectivity.
• Scaling and demonstration: Future work should explore the scalability and robustness of the developed systems under practical conditions.
• Interdisciplinary integration: Combining experimental and computational approaches will be critical to fully understand the mechanisms involved and guide catalyst design.
• International collaboration: Ongoing collaboration between host institutions will facilitate access to complementary expertise and infrastructure, accelerating progress.
At this stage, the results are primarily fundamental in nature but represent a clear step forward in the understanding and development of new reactivity paradigms. They provide a strong platform for future advances with potential long-term technological and industrial relevance.