Abstract
AbstractEquilibrium constants were determined for ligand exchange reactions of borane complexes with various oxygen, sulfur, nitrogen, and phosphorus nucleophiles in solution, and a binding affinity scale was built spanning a range of 12 orders of magnitude. While the Keq are minimally dependent on the solvent, the rate of ligand exchange varies significantly. The fastest and slowest rates were observed in THF and CDCl3, respectively. Moreover, the ligand exchange rate differs in a very broad range depending on stability of the starting complex. Binding of BH3 was found to be much more sensitive to steric factors than protonation. Comparing nitrogen bases having equal steric properties, a linear correlation of BH3 binding affinity vs. Brønsted acidity was found. This correlation can be used to quickly estimate the BH3 binding affinity of a substrate if pKa is known. Kinetic studies suggest the ligand exchange to occur as a bimolecular SN2 reaction unless other nucleophilic species were present in the reaction mixture.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.