Schneider Lab

In Crystallo Wolff Rearrangement of a Metalated Diazoester: Structural Confirmation of the Singlet Carbene Wolff-Intermediate The Wolff rearrangement (WR) is widely used for the synthesis of ketenes from diazoketones and -esters. Stepwise WR reactions are proposed to proceed through transient carbonylcarbene (R–C–C(O)–R′) in...

Check out Zejie’s paper about the crystallographic examination of a metalla-Wolff rearrangement.

pubs.acs.org/doi/10.1021/...

Exciting news. Have a great start!

Thanx!

I feel extremely honored to receive this award. It is the result of a wonderful joint journey with my team and our cooperation partners. I would like to thank them all, and all the funding agencies, from the bottom of my heart! @kit.edu @dfg.de @ercresearch.bsky.social

Transient Triplet Metallopnictinidenes M–Pn (M = PdII, PtII; Pn = P, As, Sb): Characterization and Dimerization Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M–Pn═Pn–M} (M = PdII, PtII; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M–Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Our paper on triplet pnictinidenes (P, As, Sb) with transition metal substituents is out; congrats to Marc, Nils, Tarek and Rich and thanks to all that have contributed to get a comprehensive electronic structure picture @haenisch-group.bsky.social
pubs.acs.org/doi/10.1021/...

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