Correlation of spectroscopically determined ligand donor strength and nucleophilicity of substituted pyrazoles.
The relative ligand donor strengths of 10 pyrazole-derived ligands has been determined with great accuracy, making use of the interdependence between the donor strength of the co-ligand and the (13)C NMR chemical shift of the (i)Pr(2)-bimy carbene signal in trans-[PdBr(2)((i)Pr(2)-bimy)L] complexes ((i)Pr(2)-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene; L = pyrazole-derived ligand). Even subtle variations in the substitution pattern of the pyrazole backbone up to three bonds away from the coordinating nitrogen could be detected reliably using this methodology. Alkylation experiments conducted on the pyrazoles using electrophiles of varied reactivity (ethyl bromide, ethyl iodide, and trimethyloxonium tetrafluoroborate) served as a benchmark to rank the pyrazoles in three groups of gradually increasing nucleophilicity, which correlated well with their determined donor strength.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore.
Jan Christopher
JC
Bernhammer
Han Vinh
HV
Huynh