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Synthesis, properties, and structures of chromium(VI) and chromium(V) complexes with heterocyclic nitrogen ligands

Synthesis, properties, and structures of chromium(VI) and chromium(V) complexes with heterocyclic nitrogen ligands
Synthesis, properties, and structures of chromium(VI) and chromium(V) complexes with heterocyclic nitrogen ligands
The reaction of CrO2Cl2 with 2, 2?-bipyridyl or 1, 10-phenanthroline (diimine) in CCl4 or anhydrous CH3CO2H solution, produces orange-brown diamagnetic [CrO2Cl2(diimine)]. The X-ray structure of [CrO2Cl2(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 CrO3 in CH3CO2H / conc. aqueous HCl to form bright red paramagnetic CrV complexes, [CrOCl3(diimine)]. The X-ray structure of [CrOCl3(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-bipyH2]Cl2 to a solution of CrO3 in CH3CO2H saturated with HCl gas, produces the CrV anion [2, 2?-bipyH2][CrOCl4]Cl, which loses HCl on heating in vacuo to form [CrOCl3(2, 2?-bipy)]. IR, UV/Vis, and 1H NMR spectra (CrVI 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.
chromyl chloride, chromium, nitrogen heterocycles, chromium(V) complexes
0044-2313
35-39
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Reid, Gillian and Zhang, Wenjian (2014) Synthesis, properties, and structures of chromium(VI) and chromium(V) complexes with heterocyclic nitrogen ligands. Zeitschrift Fur Anorganische Und Allgemeine Chemie, 640 (1), 35-39. (doi:10.1002/zaac.201300482).

Record type: Article

Abstract

The reaction of CrO2Cl2 with 2, 2?-bipyridyl or 1, 10-phenanthroline (diimine) in CCl4 or anhydrous CH3CO2H solution, produces orange-brown diamagnetic [CrO2Cl2(diimine)]. The X-ray structure of [CrO2Cl2(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 CrO3 in CH3CO2H / conc. aqueous HCl to form bright red paramagnetic CrV complexes, [CrOCl3(diimine)]. The X-ray structure of [CrOCl3(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-bipyH2]Cl2 to a solution of CrO3 in CH3CO2H saturated with HCl gas, produces the CrV anion [2, 2?-bipyH2][CrOCl4]Cl, which loses HCl on heating in vacuo to form [CrOCl3(2, 2?-bipy)]. IR, UV/Vis, and 1H NMR spectra (CrVI 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.

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e-pub ahead of print date: 18 November 2013
Published date: January 2014
Keywords: chromyl chloride, chromium, nitrogen heterocycles, chromium(V) complexes
Organisations: Chemistry

Identifiers

Local EPrints ID: 368640
URI: http://eprints.soton.ac.uk/id/eprint/368640
ISSN: 0044-2313
PURE UUID: 978562cd-2d94-4868-8ff0-4f05775bd767
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 06 Sep 2014 12:55
Last modified: 18 Feb 2021 16:34

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Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Wenjian Zhang

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