Research Article: UiT and HU

The first NordCO2 collaboration paper of the year is from UiT and HU, involving PhD students Aleksi (HU), Dat (UiT), and Jere (HU) from Kathrin’s and Timo’s groups. Together, they studied the the synthesis of butyrolactones from CO2 using  titanacyclopropane as mediator.

Graphical abstract: Titanium isopropoxide-mediated cis-selective synthesis of 3,4-substituted butyrolactones from CO2

Abstract:
We report a Ti(OiPr)4-mediated multicomponent reaction, which produces 3,4-substituted cis-δ-lactones from alkyl magnesium chloride, benzaldehyde and CO2. The key intermediate, titanacyclopropane, is formed in situ from Ti(OiPr)4 and a Grignard reagent, which enables 1,2-dinucleophilic reactivity that is used to insert carbon dioxide and an aldehyde. An alternative reaction route is also described where a primary alkene is used to create the titanacyclopropane. A computational analysis of the elementary steps shows that the carbon dioxide and the aldehyde insertion proceeds through an inner-sphere mechanism. A variety of cis-butyrolactones can be synthesized with up to 7 : 1 diastereoselectivity and 77% yield.

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Find a list of publications by NordCO2 members on our Publications page 🙂

Research Article: UiT

NordCO2 postdoc Ljiljana Pavlovic and PI Kathrin Hopmann have collaborated with the Hazari Group from Yale for their study on “the insertion of CO2 into palladium and nickel methyl complexes supported by RPBP […] pincer ligands”. They performed the computational analysis part of the study, where they investigated the plausible pathways for insertion.

Graphical abstract: Ligand and solvent effects on CO2 insertion into group 10 metal alkyl bonds

Title:
Ligand and solvent effects on CO2 insertion into group 10 metal alkyl bonds

Abstract:
The insertion of carbon dioxide into metal element σ-bonds is an important elementary step in many catalytic reactions for carbon dioxide valorization. Here, the insertion of carbon dioxide into a family of group 10 alkyl complexes of the type (RPBP)M(CH3) (RPBP = B(NCH2PR2)2C6H4; R = Cy or tBu; M = Ni or Pd) to generate κ1-acetate complexes of the form (RPBP)M{OC(O)CH3} is investigated. This involved the preparation and characterization of a number of new complexes supported by the unusual RPBP ligand, which features a central boryl donor that exerts a strong trans-influence, and the identification of a new decomposition pathway that results in C–B bond formation. In contrast to other group 10 methyl complexes supported by pincer ligands, carbon dioxide insertion into (RPBP)M(CH3) is facile and occurs at room temperature because of the high trans-influence of the boryl donor. Given the mild conditions for carbon dioxide insertion, we perform a rare kinetic study on carbon dioxide insertion into a late-transition metal alkyl species using (tBuPBP)Pd(CH3). These studies demonstrate that the Dimroth–Reichardt parameter for a solvent correlates with the rate of carbon dioxide insertion and that Lewis acids do not promote insertion. DFT calculations indicate that insertion into (tBuPBP)M(CH3) (M = Ni or Pd) proceeds via an SE2 mechanism and we compare the reaction pathway for carbon dioxide insertion into group 10 methyl complexes with insertion into group 10 hydrides. Overall, this work provides fundamental insight that will be valuable for the development of improved and new catalysts for carbon dioxide utilization.

Find a list of publications by NordCO2 members on our Publications page 🙂

IUPAC GBW 2022

We are putting Scandinavia on the map with our participation to IUPAC’s Global Women’s Breakfast next month. We are organising a small digital seminar together with the CO2PERATE ITN focused on diversity in our work environment, with a guest lecture and some time for discussion.

Want to know more? Learn about your own bias by taking an Implicit Association Test from the Project Implict (Havard University, USA).

You can check the details of the event as well as other events organised by NordCO2 by visiting our Activities page.

Conference: ISHHC19 (June 2022 – Oslo, Norway)

The University of Oslo is organizing the 19th International Symposium on relations between Homogeneous and Heterogeneous Catalysis (ISHHC19) on the 26th-29th June 2022, with the theme “Overarching concepts in catalysis”.

Plenary Speakers (alphabetical order):
Prof. Amy Rosensweig, Prof. Andy Borovik, Prof. Charles Sykes, Prof. Christophe Copéret, Prof. Jens Nørskov, Prof. Thomas Maschmeyer, Prof. Marc Fontecave and Prof. Wenbin Lin.

You can submit your abstract before the 30th of November 2021 at: https://www.mn.uio.no/kjemi/english/research/groups/catalysis/ishhc19/