Kaitlyn Birkhoff

Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium Synthetic access toward well-defined, monomeric s-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic complexes promoted by the Schlenk equilibrium. Ligand redistribution is significantly pronounced for the heavier s-block metals, such as calcium, which form bischelate complexes readily through traditional synthetic routes such as transmetalation, amination, and ligand exchange. Mechanistic investigation of each of these routes with phenoxyimine (ONN) ligands was explored to ascertain the fundamental parameters promote bischelate formation. Donor effects from coordinated solvent proved to be deleterious, and in an effort to circumvent bischelation, a new calcium bisamide, {Ca[N(SiMe3)2]2(diox)2}∞, was synthesized and characterized as a coordination polymer with a unique square planar geometry, rarely seen for group 2 complexes. Amination with {Ca[N(SiMe3)2]2(diox)2}∞ was found to significantly shift the Schlenk equilibrium to favor heteroleptic species, allowing for the characterization of new phenoxyimine calcium-amido complexes: [ONN1Ca–N(SiMe3)2]2(diox) and [ONN3Ca–N(SiMe3)2(diox)]∞. Subsequent studies showed that solvent exchange from the isolated dioxane complexes with THF notably shortened the stability of the complex in solution. Although steric parameters have previously been regarded as the key to the stabilization of heteroleptic calcium complexes, it is equally important to consider the donor ability of coordinated solvent ligands to achieve longer-lived heavy s-block complexes.

Happy Friday everyone! Please check out the latest paper from our group by one of our incredible students, Kaitlyn Birkhoff @kxitlyn.bsky.social !
Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium | Inorganic Chemistry pubs.acs.org/doi/10.1021/...

25.04.2025 16:21 — 👍 5    🔁 1    💬 0    📌 0

@pubs.acs.org @yruegasgroup.bsky.social

16.04.2025 21:57 — 👍 0    🔁 0    💬 0    📌 0

Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium Synthetic access toward well-defined, monomeric s-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic complexes promoted by the Schlenk equilib...

Super excited to announce that my first-author paper is now published in Inorganic Chemistry! Check it out to learn about some really cool Ca and Na complexes 🥳

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

16.04.2025 21:04 — 👍 12    🔁 2    💬 3    📌 0

Synthesis and Characterization of Well‐Defined s‐Block Bis(Carbene) Complexes Although the chemistry of monodentate N-heterocyclic carbenes (NHCs) with s-block metals has been investigated, the coordination chemistry of phenyl dicarbene (CCC = bis(diisopropylphenyl-imidazol-2-....

🚨To mark our transition to #chemsky, we are so excited to announce that our group’s first paper is now published in EJIC! Go check it out now!

Synthesis and Characterization of Well‐Defined s‐Block Bis(Carbene) Complexes
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/...

25.11.2024 18:34 — 👍 21    🔁 5    💬 3    📌 0

yes! I’ve only seen the autochem so far but it is definitely new (for my research & the world lol) Will finish the full data reduction on monday :)

17.11.2024 17:59 — 👍 0    🔁 0    💬 1    📌 0

it did! it was beautiful!

17.11.2024 17:16 — 👍 1    🔁 0    💬 1    📌 0

To celebrate my move to #chemsky, here’s a chunky crystal for your Saturday! 💎

16.11.2024 23:35 — 👍 22    🔁 0    💬 3    📌 0