Florian Mulks

Bond Dissociation Energies, Proton, Hydride, Electron Affinities, and Ionization Potentials of C1 Hydrocarbon Ions Carbon and hydrocarbons are fundamental building blocks of life. Here, we present a comprehensive computational study on the stability and reactivity of CHx±n (X = 0, 1, 2, 3, 4) species across charge states n ranging from −4 to +4 and multiplicities from singlet to quintet. We benchmark suitable methods and select CCSD(T)/aug-cc-pVQZ for computing the bond dissociation energies (BDEs), proton affinities (PAs), hydride affinities (HAs), electron affinities (EAs), and ionization potentials (IPs). We discuss observed trends in charge-dependent stability and reactivity, with implications for a fundamental understanding of carbon–hydrogen species. We believe that these data will be useful for further investigations of highly reactive hydrocarbons in unusual electronic states.

We noticed a surprising lack of data on absolutely fundamental C1 molecules. We computed a useful collection of thermodynamic data (BDE, EA, IP, HA) at the CCSD(T)/aug-cc-pVQZ level of theory to fill this gap.

Early view at J. Phys. Chem. A: pubs.acs.org/doi/10.1021/...

This model also reproduces experimental electrophilicity and nucleophilicity scales for 21 electrophiles and 20 nucleophiles, with R2 correlations of 0.98 and 0.94, respectively.

In this model, the electrophile–nucleophile interaction energy is modeled by perturbations in the chemical and external potentials of the isolated species. The GC-GPRI accurately identifies the most reactive hard and soft atoms in complex molecules with multiple reactive sites.

The GC-GPRI is derived within the zero-temperature grand canonical ensemble conceptual density-functional theory (CDFT) framework using a perturbative approach.

Abstract: The Grand Canonical General-Purpose Reactivity Indicator (GC-GPRI) is introduced as a tool for predicting reactivity and for discerning the relative electrophilicity and nucleophilicity of electrophiles and nucleophiles, respectively.

Thanks to my postdoc Yoshio Barrera for setting this colab up with his home institution. This was one of his last PhD projects with some of the great minds of conceptual density functional theory, Prof. James Anderson and Prof. Paul Ayers.

Check out our recent adventure in making simple tools for rationalizing broad chemical reactivity. The math may look a bit scary but the application is as straightforward as it gets with any standard DFT tools.

Now in early view: lnkd.in/eEnzKvuQ

Corrrection to “1,4‐Dearomatization of Pyridines and Quinolines Enabled by the Carbodication Lewis Acid” Click on the article title to read more.

Our work was the core foundation for some exciting application studies — reductions of carbodications with hydride donors! — which sadly slipped past the peer-review @angewandtechemie.bsky.social .

Thanks for the collaboration by the authors in fixing this. onlinelibrary.wiley.com/doi/10.1002/...

π‐Electron Donation at the Sulfoximidoyl Nitrogen Atom Knowledge of the physicochemical properties and the reactivity of functional groups is invaluable in organic chemistry. While substantial understanding of properties/reactivities exists for standard ...

Just accepted: Benjamin's deep dive into the "π-Electron Donation at the Sulfoximidoyl Nitrogen Atom". Pre-editing version: doi.org/10.1002/anie... Happy to contribute to this mechanistic study in a collaboration with Carsten Bolm.

Our minireview on trityl cation applications hot off the press @synthesis1969.bsky.social
— carbocations are just getting started! Check it out at:
doi.org/10.1055/a-25...

Check out Yoshio's preview article "Strained diradicaloids for σ-bond-insertion reactions: A breakthrough in drug discovery" in Chem @CellCellPress authors.elsevier.com/a/1knqg8jWHE...

We highlight Houk and Garg's exciting paper in print at Nature.
www.nature.com/articles/s41...

Check out Yoshio's preview article "Strained diradicaloids for σ-bond-insertion reactions: A breakthrough in drug discovery" in Chem @CellCellPress authors.elsevier.com/a/1knqg8jWHE...

We highlight Houk and Garg's exciting paper in print at Nature.
www.nature.com/articles/s41...

Thank you for the invitation to the special collection on modern Lewis acid chemistry, @riedellab.bsky.social @grebgroup.bsky.social and Meeta!

Thank you to EurJIC for the invitation to the EurJIC Talents collection!

One‐Step Synthesis of Donor‐Substituted Symmetric and Unsymmetric Trityl Cations from Arenes and Benzoic Acids In this study, we report that reacting electron-rich arenes and benzoic acids with trifluoromethanesulfonic anhydride gives convenient one-step and one-pot access to triphenylmethylium trifluorometha...

Congratulations to Yanick @thetimebreaker.bsky.social on the discovery of a direct access to "electron-rich" triphenylcarbenium triflates via a Friedel Crafts cascade from carboxylic acids and arenes. The paper was just accepted in EurJIC:
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/...

Recent Applications of Triphenylmethyl (Trityl) Cations in Synthesis Thieme E-Books & E-Journals

Organic Lewis acids are picking up traction!
Check out Yiwei's update short review
Recent Applications of Triphenylmethyl (Trityl) Cations in Synthesis
doi.org/10.1055/a-25...

News | mulksgrp mulksgrp at RWTH Aachen

New year, new group website:
mulksgrp.ac/post/website...

Check it out. Thanks to our student assistant for the excellent work.

We mainly improve its functionality to make it a more active space for sharing ideas and useful tutorials. See you there!

Yoshio from UNAM Mexico joins the group at @rwth.bsky.social as our first postdoc! Congratulations on the fellowship and we are excited to investigate reactions and reactivity descriptors with you!

An early Christmas present! Yiwei's update on the latest from triphenylcarbenium chemistry with a focus on applications in synthesis was published as "accepted manuscript" at Synthesis.

www.thieme-connect.com/products/ejo...

Thanks to Martin Oestreich for the invitation and fantastic process!

Big day for the group with Yanick being the first to finish a master thesis. Well done! #proudPi @RWTH
The nice trityl structures may have something to do with it, stay tuned.

This work is dedicated to the late Ralph Pearson. His ingenious HSAB principle has helped me understand chemistry tremendously and I hope this work can become half as helpful to future students.

This concept gives a better agreement with a large body of experimental results than established concepts. Simple cases can be intuitively judged, more complex ones require just three single point calculations.

I utilise the different behaviour of radicals and lone pairs to introduce a new distinguishment between hard and soft reactive sites that circumvents many problems of established concepts.

Have you ever wondered if there is a better intuitive way of understanding ambident reactivity than HSAB or orbital vs. charge-control? Kindly refer to "Hard and Soft Electrons and Holes" that is in press at Chem by Cell Press.
doi.org/10.1016/j.ch...

Our last visitor at the seminar of the Institute of Organic Chemistry of RWTH Aachen University did not have to travel far. Florian Kleemiß of the Institute of Inorganic Chemistry taught us on quantum crystallography and its uses in the investigation of chemical bonding. A very useful method!

Our coordinated gem-carbodicarbene surrogate diiminium adducts were highlighted in the organic chemistry trend report in Nachrichten aus der Chemie! That is an exciting first for us. Thank you for the honour to Urs Gellrich.

onlinelibrary.wiley.com/doi/10.1002/...

We had the please to listen to Sebastian Riedel exciting adventures in the (surprisingly applicable!) generation of halonium ions, storage of chlorine, and more. Thanks a lot for your visit at the RWTH and for the valuable discussions and advice!

I am honoured to be included in the impressive list of Thieme Chemistry Journals Award winners! Thank you for the recognition of our early independent work, which is driving us forward this year.

www.thieme.de/en/thieme-ch...

The Mulks research group including a student tuning in via Videochat.

A happy New Year from the group in Aachen. Excited to get back to discovering carbon's secrets this year!

Thank you for the invite @herreslab.bsky.social.

We shall post about our journey towards low-valent highly charged organic compounds and our effeorts toward establishing simple reactivity models.