Formation and Characterization of Zr4+ Stabilized by Neutral Tridentate Ligands in the Gas Phase

Ligated tetrapositive metal ions are rare gas-phase species which tend to form complexes with lower charges due to the high 4th ionization energies of metals. We report the observation of tetrapositive Zr(TMPDA)(3)(4+) and Zr(TMOGA)(3)(4+) complexes in the gas phase by electrospray ionization of Zr(ClO4)(4)/TMPDA and Zr(ClO4)(4)/TMOGA mixtures. The Zr4+ center in both complexes is coordinated by nine atoms from three neutral diamide ligands forming nine-coordinate twisted tricapped trigonal prismatic geometry on the basis of DFT calculations. Collision-induced dissociation of both complexes resulted in the loss of protonated ligands to form tripositive Zr(TMPDA)(TMPDA-H)(3+) and Zr(TMOGA)(TMOGA-H)(3+) products which retain the IV oxidation state of zirconium at the cost of charge reduction from 4+ to 3+ of the whole complexes. The very high 4th ionization energy of zirconium (34.34 eV) makes tetrapositive zirconium complex the most challenging tetracation to be stabilized against charge reduction in the gas phase to date.