Two-coordinate, open shell (d1 – d9) transition metal complexes with linear geometries are extremely rare but they are of increasing interest because of their unique magnetic properties.1 The use of the bulky amido ligand, -N(SiMe3)Dipp,1 successfully stabilized a series of three two-coordinate amido complexes with a linear N-M-N coordination, M{N(SiMe3)Dipp}2 {M = Fe (1),1,2 Co (2)1,2 and Ni(3)1-3}. In addition, calculations showed that attractive dispersion forces played an important role in stabilizing the unique structures. These complexes can be reduced into their M(I) oxidation states by the reaction of KC8 and 18-crown-6 to afford [K(18-crown-6)][M{N(SiMe3)Dipp}2] {M = Fe (4), Co (5) and Ni(6)}.4 DC SQUID measurement showed that the effective magnetic moments at ambient temperature are 5.89 μB (1), 5.93 μB (2), 3.22 μB (3), 5.58 μB (4), 5.60 μB (5) and 2.14 μB (6). The magnetic moments for 1 - 5 are significantly greater than the spin-only value for high-spin d6 {Fe(II)} (μeff(spin-only) = 4.90 μB), d7 {Fe(I) and Co(II)} (μeff(spin-only) = 3.87 μB) and d8 {Co(I) and Ni(II)} (μeff(spin-only) = 2.83 μB) complexes. The higher values are due to a substantial orbital contribution to their magnetic moments. Moreover, AC SQUID measurement showed that 1 behaves as a single molecule magnet under low temperature with a spin-reversal barrier, Ueff, of 181 cm-1.5 Mössbauer studies of 1 showed the largest internal magnetic field observed to date in a high spin Fe(II) complex of 162 T.6 References 1. Power, P. P. Chem. Rev. 2012, 112, 3482. 2. Lin, C.-Y.; Guo, J.-D.; Fettinger, J. C.; Nagase, S.; Grandjean, F.; Long, G. J.; Chilton, N. F.; Power, P. P. Inorg. Chem. 2013, 52, 13584. 3. Lipschutz, M. I.; Tilley, T. D. Chem. Commun. 2012, 48, 7146. 4. Lin, C. -Y.; Fettinger, J. C.; Grandjean, F.; Long, G. J.; Power, P. P. Inorg. Chem. 2014, 53, 9400. 5. Zadrozny, J. M.; Atanasov, M.; Bryan, A. M.; Lin, C.-Y.; Rekken, B.D.; Power, P. P.; Neese, F.; Long, J. R. Chem. Sci. 2013, 4, 125. 6. Bryan, A. M.; Lin, C. -Y.; Sorai, M.; Miyazaki, Y.; Hoyt, H. M.; Hablutzel, A.; LaPointe, A.; Reiff, W. M.; Power, P. P.; Schulz, C. E. Inorg. Chem. 2014, Accepted.

Magnetic and spectroscopic properties of linear two-coordinate transition metal complexes

249th National Meeting (2015)

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