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Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands
Author(s) -
Levason William,
Reid Gillian,
Zhang Wenjian
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300482
Subject(s) - diimine , chromium , chemistry , medicinal chemistry , adduct , octahedron , phosphine , inorganic chemistry , stereochemistry , crystallography , crystal structure , organic chemistry , catalysis
The reaction of CrO 2 Cl 2 with 2, 2′‐bipyridyl or 1, 10‐phenanthroline (diimine) in CCl 4 or anhydrous CH 3 CO 2 H solution, produces orange‐brown diamagnetic [CrO 2 Cl 2 (diimine)]. The X‐ray structure of [CrO 2 Cl 2 (2, 2′‐bipy)] shows a six‐coordinate central chromium(VI) atom with cis ‐dioxo groups trans to the diimine. In contrast, the diimines react with CrO 3 in CH 3 CO 2 H / conc. aqueous HCl to form bright red paramagnetic Cr V complexes, [CrOCl 3 (diimine)]. The X‐ray structure of [CrOCl 3 (2, 2′‐bipy)] shows a six‐coordinate central chromium atom with mer ‐chlorines and the diimine trans to O/Cl. The addition of [2, 2‐bipyH 2 ]Cl 2 to a solution of CrO 3 in CH 3 CO 2 H saturated with HCl gas, produces the Cr V anion [2, 2′‐bipyH 2 ][CrOCl 4 ]Cl, which loses HCl on heating in vacuo to form [CrOCl 3 (2, 2′‐bipy)]. IR, UV/Vis, and 1 H NMR spectra (Cr VI only) are reported for the new complexes. Attempts to extend these routes to oxygen donor ligands, including ethers and phosphine oxides, were unsuccessful. The diimine complexes are the first structurally autheticated adducts of chromium(VI) and (V) oxide‐chlorides with neutral ligands.