Final answer:
Mg²+ is crucial in the hexokinase reaction for shielding negative charges on ATP's phosphate groups and increasing the electrophilicity of the terminal phosphorus atom, enabling its efficient phosphorylation of glucose.
Step-by-step explanation:
In the hexokinase reaction, MgATP²⁻ is the substrate, rather than ATP⁴⁻, because the presence of Mg²⁻ is critical for the activity of the enzyme. Firstly, Mg²⁻ shields the negative charges on the phosphate groups of ATP, which would otherwise repel the nucleophilic attack by the glucose –OH group. Secondly, the Mg²⁻ complex increases the electrophilicity of the terminal (gamma) phosphorus atom of ATP, making it more accessible to nucleophilic attack, thereby facilitating the transfer of the phosphate group to glucose to form glucose-6-phosphate, the first step of glycolysis.