The versatile coordination behavior of the PNP ligands 1A (2,6-bis[(di-tert-butylphosphino)methyl]pyridine) and 1B (2,6-bis[(diphenylphosphino)methyl]pyridine) to Cu-I is described, whereby a hemilabile interaction of the pyridine N-donor atom to the copper center resulted in a rare T-shaped complex with 1A, while with 1B also a tetracoordinated species could be isolated. Theoretical calculations support the weak interaction of the pyridine N donor in 1A with the Cu center.