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Studies on chromium(III) and vanadium(III) complexes with crown ether and crown thioether coordination - Synthesis, properties and structural systematics

Studies on chromium(III) and vanadium(III) complexes with crown ether and crown thioether coordination - Synthesis, properties and structural systematics
Studies on chromium(III) and vanadium(III) complexes with crown ether and crown thioether coordination - Synthesis, properties and structural systematics
A series of six-coordinate chloro Cr-III and V-III complexes involving crown ether, crown thioether and mixed ether/thioether crowns, [MCl3(crown)] (M = Cr or V, crown = 12-crown-4, 15-crown-5,18-crown-6, [12]aneS(4), [15]aneS(5), [9]aneS(2)O, [15]aneS(2)O(3), [18]aneS(3)O(3)) has been prepared by the reaction of [MCl3(thf)(3)] with rigorously dried crown in anhydrous CH2Cl2. In the presence of small amounts of water the monoaquo species [MCl3(H2O)(15-crown-5)] and [MCl3(H2O)(18-crown-6)] are obtained. The products have been characterised by IR and UV/Visible spectroscopy, microanalyses and for [CrCl3(H2O)(18-crown-6)], [VCl3(H2O)(15-crown-5)] and [CrCl3([15]aneS(5))], by X-ray crystallography. The unexpected affinity of specifically the 15-crown-5 and 18-crown-6 complexes to pick up H2O is rationalised in terms of the strain within the two adjacent five-membered chelate rings in the anhydrous (kappa(3)-coordinated) species, and a wider survey of the structures reported for six-coordinate M-III crown complexes (M = Sc - Cr) with RECH2CH2ER (E = 0 or S) reveals that while the S-M-S angles in five-membered chelate rings are typically around 82 degrees, those involving O-M-O are very substantially more acute at around 75 degrees. Thus, the [MCl3 (kappa(3)-crown ether)] complexes are much less stable and can alleviate some of this significant ring strain by switching to kappa(2)-crown coordination with the H2O ligand completing the six coordination. In contrast, the crown thioether complexes have much less tendency to do this and hence appear to be more stable. Furthermore, using the structurally related (dimethylene linkages) mixed thia/oxa crowns to probe the M-O vs. M-S binding competitively, strongly indicates that the Cr-III and V-III preferentially coordinate to the thioether rather than the ether donor atoms, contrary to normal expectation based upon HSAB theory.
chromium, crown ether, thioether macrocycle, vanadium transition-metal complexes, polyether sulfide syntheses, crystal-structure, spectroscopic characterization, scandium(iii), macrocycles, trimerization, products, ethylene, chloride
1434-1948
4399-4406
Beard, C.D.
3428eb70-d998-4b45-a31b-f47413269620
Carr, L.
1fdb57b5-1797-429a-9da5-c84e6cece770
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Evans, J.
05890433-0155-49fe-a65d-38c90ea25c69
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Norman, L.D.
932889d5-d913-4c10-9c0f-766bba77e204
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Beard, C.D.
3428eb70-d998-4b45-a31b-f47413269620
Carr, L.
1fdb57b5-1797-429a-9da5-c84e6cece770
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Evans, J.
05890433-0155-49fe-a65d-38c90ea25c69
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Norman, L.D.
932889d5-d913-4c10-9c0f-766bba77e204
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Beard, C.D., Carr, L., Davis, M.F., Evans, J., Levason, W., Norman, L.D., Reid, G. and Webster, M. (2006) Studies on chromium(III) and vanadium(III) complexes with crown ether and crown thioether coordination - Synthesis, properties and structural systematics. European Journal of Inorganic Chemistry, (21), 4399-4406. (doi:10.1002/ejic.200600573).

Record type: Article

Abstract

A series of six-coordinate chloro Cr-III and V-III complexes involving crown ether, crown thioether and mixed ether/thioether crowns, [MCl3(crown)] (M = Cr or V, crown = 12-crown-4, 15-crown-5,18-crown-6, [12]aneS(4), [15]aneS(5), [9]aneS(2)O, [15]aneS(2)O(3), [18]aneS(3)O(3)) has been prepared by the reaction of [MCl3(thf)(3)] with rigorously dried crown in anhydrous CH2Cl2. In the presence of small amounts of water the monoaquo species [MCl3(H2O)(15-crown-5)] and [MCl3(H2O)(18-crown-6)] are obtained. The products have been characterised by IR and UV/Visible spectroscopy, microanalyses and for [CrCl3(H2O)(18-crown-6)], [VCl3(H2O)(15-crown-5)] and [CrCl3([15]aneS(5))], by X-ray crystallography. The unexpected affinity of specifically the 15-crown-5 and 18-crown-6 complexes to pick up H2O is rationalised in terms of the strain within the two adjacent five-membered chelate rings in the anhydrous (kappa(3)-coordinated) species, and a wider survey of the structures reported for six-coordinate M-III crown complexes (M = Sc - Cr) with RECH2CH2ER (E = 0 or S) reveals that while the S-M-S angles in five-membered chelate rings are typically around 82 degrees, those involving O-M-O are very substantially more acute at around 75 degrees. Thus, the [MCl3 (kappa(3)-crown ether)] complexes are much less stable and can alleviate some of this significant ring strain by switching to kappa(2)-crown coordination with the H2O ligand completing the six coordination. In contrast, the crown thioether complexes have much less tendency to do this and hence appear to be more stable. Furthermore, using the structurally related (dimethylene linkages) mixed thia/oxa crowns to probe the M-O vs. M-S binding competitively, strongly indicates that the Cr-III and V-III preferentially coordinate to the thioether rather than the ether donor atoms, contrary to normal expectation based upon HSAB theory.

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More information

Published date: 2006
Keywords: chromium, crown ether, thioether macrocycle, vanadium transition-metal complexes, polyether sulfide syntheses, crystal-structure, spectroscopic characterization, scandium(iii), macrocycles, trimerization, products, ethylene, chloride

Identifiers

Local EPrints ID: 44377
URI: http://eprints.soton.ac.uk/id/eprint/44377
ISSN: 1434-1948
PURE UUID: 5ddfd914-a4c1-4ca4-ab0e-609914e337df
ORCID for W. Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for G. Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 02 Mar 2007
Last modified: 05 Nov 2019 02:08

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Contributors

Author: C.D. Beard
Author: L. Carr
Author: M.F. Davis
Author: J. Evans
Author: W. Levason ORCID iD
Author: L.D. Norman
Author: G. Reid ORCID iD
Author: M. Webster

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