Work

Potassium Isopropyl(trimethylsilyl)amide and Potassium tert -Butyl(trimethylsilyl)amide: Solvent-Dependent Solution Structures and Reactivities

Year: 2025

Type: article

Abstract: Potassium isopropyl(trimethylsilyl)amide (KPTA) and potassium tertbutyl(trimethylsilyl)amide (KBTA) were prepared as stable 1.0 M stock solutions in Et3N or isolable crystalline solids. A combination of the Method of Continuous Variations and a heavy reliance on 29Si NMR spectroscopy revealed solventdependent dimers and monomers. DFT computations offered insights into the solvation. Weakly coordinating solvents such as toluene and triethylamine afford dimers. In THF, KPTA is dimeric whereas KBTA is dimeric at low THF concentration and monomeric in neat THF. Chronic and often poorly understood loss of the 29Si resonance made a broadly based, systematic study difficult and may have obscured deaggregation or ionization. Reactivity was probed using orthometalations by KBTA, which pressed the limits of its basicity and probably impacted the yields in some cases.

Source: Organometallics

DOI: 10.1021/acs.organomet.5c00013

Authors: Jesse A. Spivey, David B. Collum

Institution: Cornell University

Language: English

Topic: Coordination Chemistry and Organometallics

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Institute of General Medical Sciences

Award: G8040758045