Substituent effects on the light-induced C–C and C–Br bond activation in (bisphosphine)(η2-tolane)Pt0 complexes. A TD-DFT study
Literature Information
Daniel Escudero, Mariana Assmann, Anne Pospiech, Wolfgang Weigand, Leticia González
A theoretical study of the steric and electronic effects of different substituents on the electronic ground and excited states of (bisphosphine)(η2-tolane)Pt0 complexes is presented. A natural-bond-order (NBO) analysis has been performed to describe the bonding nature of the “hapto-like” coordination of the Pt atom to the alkyne bond of the tolane group. The results show an important contribution of the π-back donation in all complexes, amounting to half of the energy associated to the σ-bonding interaction. A TD-DFT study of the absorption spectra helps rationalizing the photochemistry of the complexes. Metal–ligand charge transfer (MLCT) transitions from the Pt atom to the alkyne are assigned as the photochemical “active” states responsible for C–C bond cleavage. Electronic excitations to the σ* orbital of the C–Br bond are involved in C–Br bond activation. It is shown that both steric and electronic effects play an important role in determining the presence of these electronic excitations.
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Physical Chemistry Chemical Physics

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.











![(4R,5S,6S)-3-({(3S,5S)-5-[(3-Carboxyphenyl)carbamoyl]-3-pyrrolidinyl}sulfanyl)-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid structure (4R,5S,6S)-3-({(3S,5S)-5-[(3-Carboxyphenyl)carbamoyl]-3-pyrrolidinyl}sulfanyl)-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid structure](https://static.chemtradehub.com/structs/153/153832-46-3-b2e0.webp)


