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Our new Harder Group Poster 2024
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Harder-Research
1,424 posts
- 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. @Nature @UniFAU nature.com/articles/s4158…
- 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? bit.ly/3eywhMG @Science @FAU @JakeYeston
- After Mg-Mg and Be-Be: TIME FOR HEAVY METAL! The Ca-Ca bond is weak and likely forms untamed radicals. Here we present first Mg-Ca, Mg-Sr and Mg-Ba bonds. There is a bonus Na. THREE-IN-A-ROW! @NatureSynthesis @FAU nature.com/articles/s4416…
- Ba(0) SYNTHON: Ba metal does not react with anthracene. Using Metal-Vapor-Synthesis we prepared a Ba-anthracenide, a cyclic octamer. Like Bogdanovic's Mg-anthracene, it reacts like a soluble form of atomic Ba(0). Olie's first paper in our group shorturl.at/eisL2 @angew_chem
- AND HERE ANOTHER ONE FOR CAMERON'S BIG 60! Ball-milling produces deep purple Mg radicals that react with H2 or reduce benzene. Extraction with pentane gave essentially pure Mg(I) dimers. Ball-milling = COOL! onlinelibrary.wiley.com/doi/10.1002/za… Hang on Cameron!
- LiAlH4 and Fe: TOGETHER STRONG! LiAlH4 is known for stoichiometric reduction of C=O and C=N. Just a pinch of iron transforms LiAlH4 into an highly active alkene and arene catalyst. This one is for Lanthanide Peter (the southern hemisphere one) @peterjunk2 onlinelibrary.wiley.com/doi/10.1002/an…
- JUST ADD A PINCH OF IRON: Mg hydride complexes do not catalyze benzene hydrogenation. Finely divided Fe(0) doesn't either. But the combination gives a highly potent catalyst!!! The Fe-surface activates benzene for reduction by Mg hydride. @NatureComms rdcu.be/cPimn
- The Mg-Ca bond: DOES IT EXIST? Low-valent Mg-Mg complexes ala @Jones_Research are mildly reducing. Ca-Ca complexes even reduce N2. What about mixed-metal Mg-Ca complexes? Thx to the reviewers for improving the manuscript! @ChemicalScience pubs.rsc.org/en/content/art…
- ALKALINE-EARTH POWER @FAU: coupling of benzene to biphenyl and H2 generally involves Pd mediation or strong Lewis acids and harsh conditions. Latter Scholl reaction follows cationic pathways. We show anionic benzene-benzene coupling: bit.ly/3GKM2ye
- A LOT OF MONEY FOR CHEAP METALS: Happy that our group has been awarded an ERC-ADVANCED GRANT extending our unique chemistry on main group M(0) chemistry. We thank the many reviewers that trust us continuing COOL (OR HOT?) CHEMISTRY. We won’t disappoint you! @FAU #ERCAdG
- WEAKLY COORDINATING ANIONS: We like BIG ligands! Here is a superbulky R2N(-) ligand. The amine R2NH cannot even be deprotonated with a superbase BuLi/KOtBu! But with Cs metal we managed it. A new halogen-free weakly-coordinating anion???@ChemicalScience shorturl.at/djmuG
- BENZENE(4-): Aromatic but not so stable - high charge & full antibonding orbitals! Most C6H6(4-) claims are highly controversial. We report proof for C6H6(4-) by comparing structures of Ca/Yb & Sr/Sm pairs that are normally perfectly matching @angew_chem shorturl.at/glrx1
- REDUCTION WITH THE BALL-MILL: Isolation of low-valent LMg radicals by cleavage of LMg-MgL so far failed. Key to isolation of a labile LMg radical is the ball-mill AND a pi-accepting CAAC ligand, mobbing up most of the spin density. onlinelibrary.wiley.com/doi/10.1002/an…
