Here we investigate the mechanism for explosive synchronization (ES) of a complex neural network composed of nonidentical neurons and coupled by Newman-Watts small-world matrices. We find a range of nonlocal connection probabilities for which the network displays an abrupt transition to phase synchronization, characterizing ES. The mechanism behind the ES is the following: As the coupling parameter is varied in a network of distinct neurons, ES is likely to occur due to a bistable regime, namely a chaotic nonsynchronized and a regular phase-synchronized state in the phase space. In this case, even small coupling changes make possible a transition between them. The onset of ES occurs via a saddle-node bifurcation of a periodic orbit that leads the network dynamics to display a locally stable phase-synchronized state. The presence of this regime is accompanied by a hysteresis loop on the network dynamics as the coupling parameter is adiabatically increased and decreased. The end of the hysteresis loop is marked by a frontier crisis of the chaotic attractor which also determines the end of the coupling strength interval where ES is possible.