Octa-coordinated alkaline earth metal–dinitrogen complexes M(N(2))(8) (M=Ca, Sr, Ba)

We report the isolation and spectroscopic identification of the eight-coordinated alkaline earth metal–dinitrogen complexes M(N(2))(8) (M=Ca, Sr, Ba) possessing cubic (O(h)) symmetry in a low-temperature neon matrix. The analysis of the electronic structure reveals that the metal-N(2) bonds are mainly due to [M(d(π))]→(N(2))(8) π backdonation, which explains the observed large red-shift in N-N stretching frequencies. The adducts M(N(2))(8) have a triplet ((3)A(1g)) electronic ground state and exhibit typical bonding features of transition metal complexes obeying the 18-electron rule. We also report the isolation and bonding analysis of the charged dinitrogen complexes [M(N(2))(8)](+) (M=Ca, Sr).