Chemoselective quantum control of carbonyl bonds in Grignard reactions using shaped laser pulses

Literature Information

Publication Date 2010-11-16
DOI 10.1039/C0CP01657H
Impact Factor 3.676
Authors

Caroline Gollub, Markus Kowalewski, Sebastian Thallmair, Regina de Vivie-Riedle


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Abstract

Grignard reactants like methylmagnesium chloride are not selective with respect to different carbonyl bonds. We present a theoretical study where shaped laser pulses are utilized to prefer specific bonds in a mixture of more than one carbonyl reactant. A mixture of cyclohexanone and cyclopentanone has been chosen as a representative example. The light pulse is supposed to provide the activation energy and to adopt the function of a protecting group. The control aim is to stretch exclusively the C–O bond of one compound to the length required in the Grignard transition state. To guarantee an experimentally realizable bandwidth for the unshaped pulse, we use our recently developed optimal control theory algorithm, which allows the simultaneous optimization of the light field in the time and frequency domain. Highly selective picosecond control pulses could be optimized in the infrared regime suggesting that laser assisted chemoselectivity is possible to a large extent. To obtain control not only on the final product but also on the excitation mechanism, various initial conditions and frequency restrictions were investigated.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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