News
May 2021
Combining mixing metals with making cations. Our latest contribution by Alexander and Jonathan in Angewandte Chemie.
HETEROBIMETALLIC CATIONS: Mg, Zn, Al, Ga cocktails. Choice of metals strongly influences M-M bond character, stability and reactivity. Their cationic nature is key to facile RT C-F bond cleavage via a new mechanism. (even in p-Me-C6H4-F!) http://bitly.ws/dnZG
May 2021
Katharina reports on Lewis base-free cationic complexes of the largest alkaline earth metals Sr and Ba! A BIG challenge to stabilize these BIG metal cations!
“NAKED” STRONTIUM AND BARIUM CATIONS: After Lewis base-free cationic Mg and Ca complexes, we now finally also have the big ones “naked”. (NacNac)Ba+ interacts with a large pi-system. (R2N)Ba+ is sandwiched between toluenes. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ej
April 2021
The group made it into NATURE!!! The fantastic cooperative atmosphere within our group enabled isolation of first Mg(0) complexes. Congratulations to all!
ANIONIC MAGNESIUM: Turning R-Mg-I into R-Mg-Na which reacts as a Mg nucleophile RMg(-) Na(+). Heating gave spontaneous Na(+) --> Na(0) reduction (!) and RMgMgMgR, a long sought-after intermediate in Grignard formation. https://nature.com/articles/s4158
March 2021
The group made it into SCIENCE!!! It was a hard job to develop this OCTOPUSSY ligand but in the end, hard work always pays off! Congratulations to the chemists who made this giant breakthrough possible!
CRACKING N≡N WITH Ca: Octopussy strikes again! Attempts to isolate a Ca(I) complex gave reduction of aromatic solvents. Thx to many arms complexes are soluble in alkanes. Now N2 is reduced. d-Orbitals on Ca? Is LCaCaL possible? https://bit.ly/3eywhMG
January 2021
Interesting to see how the two twin metals Mg and Zn can be the same but also so different. Great work from Alexander!
Mg AND Zn: THE SAME BUT DIFFERENT! A first “naked” cationic (BDT)Zn+ complex eagerly forms bonds to arenes and halobenzenes. Despite similar Mg2+ and Zn2+ size, ligand bonding can be quite different due to hard/soft differences. https://pubs.acs.org/doi/10.1021/ac
December 2020
Ever heard of the sigma-hole? Here we show a map. Congratulations Alex and Jonathan on this combined experimental/theoretical project.
Interesting to see MAPPING THE SIGMA-HOLE: Complexation of PhF, PhCl, PhBr, PhI with highly Lewis-acidic Mg cations. Mg…X-Ph angles decrease from F > Cl > Br > I due to the halogen sigma-hole. In all cases there is considerable C-X bond activation. https://pubs.rsc.org/en/content/art
November 2020
Can main group metals also bind alkenes? Katharina and Alexander say: YES!
UNSUPPORTED MAGNESIUM-ALKENE COORDINATION: Intramolecular s-block metal-alkene complexes are known. We present first INTERMOLECULAR examples. Mg-alkene bonding leads to C=C polarization. Although weak, it is crucial in catalysis. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202004716
November 2020
Why using a complicated ligand when just metal is enough? Johannes demonstrates that Ba metal alone is a fantastic hydrogenation catalyst.
NO LIGANDS – JUST METAL: 200 years after Döbereiner’s Pt and 100 years after Sabatier’s Ni, metallic Ba is found to be an all-round hydrogenation catalyst. We propose a DUAL SITE mechanism in which Ba(0) and BaH2 are crucial. https://onlinelibrary.wiley.com/doi/10.1002/an
June 2020
ROYAL SOCIETY MAIN GROUP CHEMISTRY PRIZE
The Boss wins prestigious Award! Or actually the Harder group won. Thanks to all students: past, present, future. https://rsc.org/awards-funding/awards/2020-winners/professor-sjoerd-harder/