Atomic partial charges are local, model-dependent descriptors that often fail to capture the global electrostatic environment governing noncovalent interactions and reactivity. Here, through calculations and NMR experiments, the authors evaluate atomic charges and molecular electrostatic potential (ESP) extrema in trisubstituted silanes in the gas phase and in benzene and o-dichlorobenzene solvents, showing that the ESP at Si–H is a more decisive predictor of molecular reactivity, whereas local charges alone are misleading.
- Vítězslav Hrubý
- Debashree Manna
- Pavel Hobza
