Category: General

We are doing it again! We are happy to participate to this year’s edition of the Global Women’s Breakfast event, and take the opportunity to reflect on topics relevant to our locations in the Nordic countries. This year, Associate Professor Melina Duarte from the Department of Philosophy at UiT has agreed to give us a talk about the concept of diversity in our environment, we are looking forward to it!

In addition to the guest lecture, it is our pleasure to invite you to physical breakfasts at four of our locations: Helsinki, Oslo, Reykjavík, and Tromsø!

Details and registration for the digital event are available on our Activities page 🙂

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.

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.

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

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.

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 S_E2 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 🙂

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.