We use large scale ab initio calculations to investigate the valence and valence-Rydberg quintet states of N(2), their transition moments and their spin-orbit couplings to the close lying triplet electronic states. In addition to the A(') (5)Sigma(+)(g) and the C(') (5)Pi(ui) states already known, we identify two weakly bound states (2 (5)Sigma(+)(g) and 2 (5)Pi(u)) at similar to 95 300 and 106 200 cm(-1) above N(2)(X (1)Sigma(+)(g), v=0). The other quintets are viewed to be repulsive in nature. Our potentials and couplings are used later to derive a set of accurate spectroscopic data for these quintets, their spin-orbit constants, and to elucidate the quintet-triplet dynamics and the role of these newly identified quintets for the production of cold atomic nitrogen.