Ab initio MP2/aug'-cc-pVTZ calculations have been carried out in search of equilibrium structures with (PCl)-Cl-... pnicogen bonds or halogen bonds on the potential energy surfaces H2FP:ClY for Y = F, NC, Cl, CN, CCH, CH3, and H. Three different types of halogen-bonded complexes with traditional, chlorine-shared, and ion-pair bonds have been identified. Two different pnicogen-bonded complexes have also been found on these surfaces. The most electronegative substituents F and NC form only halogen-bonded complexes, while the most electropositive substituents CH3 and H form only pnicogen-bonded complexes. The halogen-bonded complexes involving the less electronegative groups Cl and CN are more stable than the corresponding pnicogen-bonded complexes, while the pnicogen-bonded complexes with CCH are more stable than the corresponding halogen-bonded complex. Traditional halogen-bonded complexes are stabilized by charge transfer from the P lone pair to the CI-A sigma* orbital, where A is the atom of Y directly bonded to Cl. Charge transfer from the Cl lone pair to the P-F sigma* orbital stabilizes pnicogen-bonded complexes. As a result, the H2FP unit becomes positively charged in halogen-bonded complexes and negatively charged in pnicogen-bonded complexes. Spin spin coupling constants (Ix)J(P-Cl) for complexes with traditional halogen bonds increase with decreasing P CI distance, reach a maximum value for complexes with chlorine-shared halogen bonds, and then decrease and change sign when the bond is an ion-pair bond. (1)PAJ (P-CI) coupling constants across pnicogen bonds tend to increase with decreasing P-Cl distance.