An ab initio multireference study of reductive eliminations from organoferrates(iii) in the gas-phase: it is all about the spin state

Literature Information

Publication Date 2020-07-20
DOI 10.1039/D0CP02834G
Impact Factor 3.676
Authors

Abhishek Khedkar, Michael Roemelt


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Abstract

Organoferrates(III) of the composition [FeR3R′]− have previously been identified in multiple studies as reaction intermediates during Fe-mediated cross coupling reactions. They are readily formed under reaction conditions and are able to efficiently eliminate cross coupling products which is a key step of the total reaction. However, only little is known about the electronic and structural properties of these organoferrates(III) and the mechanistic details of the reductive elimination. In this work modern ab initio electronic structure methods on the basis of the density matrix renormalization group (DMRG) are used to study the properties and reactivity of a set of eight organoferrates(III) with composition [Ph3FeR]− that have been investigated previously by mass-spectrometry experiments. The presented results provide a detailed picture about the reaction mechanism that explains the experimentally observed chemoselectivity in the gas-phase for the majority of cases. An interesting aspect of the proposed mechanism is the central role of the total spin which changes in the course of the reaction and governs the type of reaction mechanism. Eventually the applied computational procedures are thoroughly discussed in view of the conceptual and technical difficulties that were faced during the conducted studies.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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