[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
This publication has 23 references indexed in Scilit:
- Nitridomanganese(V) and -(VI) Complexes Containing Macrocyclic Amine LigandsJournal of the American Chemical Society, 1998
- Stereoelectronic Aspects of Inter-Metal Nitrogen Atom Transfer Reactions between Nitridomanganese(V) and Chromium(III) PorphyrinsInorganic Chemistry, 1997
- Nitridomanganese(V) Complexes: Design, Preparation, and Use as Nitrogen Atom-Transfer ReagentsAccounts of Chemical Research, 1997
- Synthesis and Characterization of Six-Coordinate Nitrido Complexes of Vanadium(V), Chromium(V), and Manganese(V). Isolation of a Dinuclear, Mixed-Valent μ-Nitrido Chromium(III)/Chromium(V) SpeciesInorganic Chemistry, 1996
- Nitrido Complexes of Transition MetalsAngewandte Chemie International Edition in English, 1992
- Thermodynamic and kinetic aspects of two- and three-electron redox processes mediated by nitrogen atom transferJournal of the American Chemical Society, 1991
- The nitrogen atom transfer reactivity of nitridomanganese(V) porphyrins with chromium(III) porphyrinsJournal of the American Chemical Society, 1989
- Formation of nitridoiron(V) porphyrins detected by resonance Raman spectroscopyJournal of the American Chemical Society, 1988
- Activation and transfer of nitrogen from a nitridomanganese(V) porphyrin complex. Aza analog of epoxidationJournal of the American Chemical Society, 1983
- The nephelauxetic series of ligands corresponding to increasing tendency of partly covalent bondingJournal of Inorganic and Nuclear Chemistry, 1958