[Cr(N)Cl4]2-: A Simple Nitrido Complex Synthesized by Nitrogen-Atom Transfer
- 9 October 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (44) , 13348-13349
- https://doi.org/10.1021/ja0371000
Abstract
A new general route to nitrido complexes of Cr(V) based on nitrogen-atom transfer from Mn(N)(salen) to labile CrCl3(THF)3 is presented. By this approach, the simplest nitrido complex of a first row transition metal, [Cr(N)Cl4]2-, has been synthesized and isolated. [[N(CH3)4]2[Cr(N)Cl4]·H2O crystallizes in the cubic space group Fm-3m with disordered anions. Cr−N is 1.555(19) Å, Cr−Cl is 2.2912(16) Å, and N−Cr−Cl is 101.24(4)°. The orbital splitting scheme of [Cr(N)Cl4]2- is extreme with the dx2-y2 orbital 10 000 cm-1 lower in energy than the degenerate {dzx, dyz} set of orbitals destabilized by π-bonding with the nitrido ligand. Hydrolysis of [Cr(N)Cl4]2 preserves the {Cr⋮N}2+ moiety.Keywords
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