Structure of a dinickel(II)-dithiolate bridged macrocyclic complex synthesised via a novel solvent-assisted disulfide cleavage reaction
Structure of a dinickel(II)-dithiolate bridged macrocyclic complex synthesised via a novel solvent-assisted disulfide cleavage reaction
The reaction of 2,6-diformyl-4-methylphenyl disulfide with [Ni(tn)3]Cl2 (tn = 1,3-diaminopropane), in methanol and in the presence of NaBPh4 resulted in the isolation of [Ni2(L1)](DMF)2(BPh4)2 (I), (L1 = 15,95-dimethyl-3,7,11,15-tetraaza-1,9(1,3)-dibenzenacyclohexadecaphane-2,7,10,15-tetraene-12,92-bis(thiolate). This reaction represents a 2-electron solvent assisted reduction of the disulfide bond to form two thiolate ligands where methanol is converted to formaldehyde and the two nickel centres remained in the + 2 oxidation state. The crystal structure of I showed the two nickel(II) atoms are bridged by two thiolates in a binuclear Ni2S2 core inside of a macrocyclic framework. The IR spectrum showed a band at 1625 cm−1, assigned to the imine ν(C [dbnd]N) stretch of the macrocyclic ligand, and bands at 734, 706 cm−1, are assigned to the tetraphenylborate counter ions. This is the first example of solvent assisted S–S bond cleavage being used to prepare a dicompartmental macrocyclic complex.
Dicompartmental macrocycle, Nickel(II)-thiolate, Robson type macrocycle, Solvent assisted disulfide cleavage, X-ray diffraction
Mendicute-Fierro, Claudio
a1f6ddac-3db7-49e8-a4e0-549ef49a05c9
Smith, Paul D.
1aebdfbe-633d-469b-b812-e33fed47ff9b
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
15 January 2023
Mendicute-Fierro, Claudio
a1f6ddac-3db7-49e8-a4e0-549ef49a05c9
Smith, Paul D.
1aebdfbe-633d-469b-b812-e33fed47ff9b
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Mendicute-Fierro, Claudio, Smith, Paul D. and Light, Mark E.
(2023)
Structure of a dinickel(II)-dithiolate bridged macrocyclic complex synthesised via a novel solvent-assisted disulfide cleavage reaction.
Polyhedron, 230, [116222].
(doi:10.1016/j.poly.2022.116222).
Abstract
The reaction of 2,6-diformyl-4-methylphenyl disulfide with [Ni(tn)3]Cl2 (tn = 1,3-diaminopropane), in methanol and in the presence of NaBPh4 resulted in the isolation of [Ni2(L1)](DMF)2(BPh4)2 (I), (L1 = 15,95-dimethyl-3,7,11,15-tetraaza-1,9(1,3)-dibenzenacyclohexadecaphane-2,7,10,15-tetraene-12,92-bis(thiolate). This reaction represents a 2-electron solvent assisted reduction of the disulfide bond to form two thiolate ligands where methanol is converted to formaldehyde and the two nickel centres remained in the + 2 oxidation state. The crystal structure of I showed the two nickel(II) atoms are bridged by two thiolates in a binuclear Ni2S2 core inside of a macrocyclic framework. The IR spectrum showed a band at 1625 cm−1, assigned to the imine ν(C [dbnd]N) stretch of the macrocyclic ligand, and bands at 734, 706 cm−1, are assigned to the tetraphenylborate counter ions. This is the first example of solvent assisted S–S bond cleavage being used to prepare a dicompartmental macrocyclic complex.
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Accepted/In Press date: 21 November 2022
e-pub ahead of print date: 23 November 2022
Published date: 15 January 2023
Additional Information:
Funding Information:
We thank Manchester Metropolitan University for the studentship to CMF.
Publisher Copyright:
© 2022 The Authors
Keywords:
Dicompartmental macrocycle, Nickel(II)-thiolate, Robson type macrocycle, Solvent assisted disulfide cleavage, X-ray diffraction
Identifiers
Local EPrints ID: 474569
URI: http://eprints.soton.ac.uk/id/eprint/474569
ISSN: 0277-5387
PURE UUID: 8d9327d8-e990-44c0-be7c-63d3de9ebb3b
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Date deposited: 27 Feb 2023 17:35
Last modified: 18 Mar 2024 02:50
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Author:
Claudio Mendicute-Fierro
Author:
Paul D. Smith
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