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Half a grid is better than no grid: competition between 2,2?:6?,2??-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(ii)

Half a grid is better than no grid: competition between 2,2?:6?,2??-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(ii)
Half a grid is better than no grid: competition between 2,2?:6?,2??-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(ii)
The reaction between Cu(NO(3))(2)center dot 3H(2)O, 2,2':6',2 ''-terpyridine(tpy) and 3,6-di(pyrid-2-yl) pyridazine (1) in a 2 : 2 : 1 molar equivalent ratio in aqueous MeCN in the presence of excess NH(4)PF(6) leads to competition between the assembly of the dinuclear half-grid [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O and the mononuclear complex [Cu(1)(2)(OH(2))][PF(6)](2). The yield of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O has been optimized using microwave conditions. [Cu(1)2(OH(2))][PF(6)](2) can be selectively produced by treating Cu(NO(3))(2)center dot 3H(2)O with 1 (1:2 molar equivalents) in aqueous MeCN in the presence of NH(4)PF(6). The single crystal structures of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 4MeNO(2) and [Cu(1)(2)(OH(2))][PF(6)](2) are presented. In the [Cu(2)(1)(tpy)(2)](4+) cation, ligand 1 bridges the two copper(II) centres, each of which is further coordinated by a tpy ligand. The copper(II) coordination geometry is closely associated with the arrangement of the two tpy ligands which engage in efficient face-to-face p-stacking. Magnetic data for crystalline [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 4MeNO(2) are consistent with a weak antiferromagnetic interaction between the two copper(II) centres. EPR spectroscopic data for a powder sample of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O are consistent with the dinuclear structure, but in frozen DMF and DMSO solutions, the data indicate that the dinuclear structure of [Cu(2)(1)(tpy)(2)](4+) is not preserved.
0300-9246
2337-2343
Constable, Edwin C.
d7da4205-ec75-47b5-a666-9ce90618069b
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd
Housecroft, Catherine E.
b63e2e1e-5ab0-4c20-858f-102cd71e5128
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Palivan, Cornelia G.
75393280-eae2-4ea3-a417-e185970ee139
Price, Jason R.
b4b3362d-8a02-4446-8e83-302ae792f6b0
Zampese, Jennifer A.
0114ba0f-5329-43a4-b991-ab68e15adee9
Constable, Edwin C.
d7da4205-ec75-47b5-a666-9ce90618069b
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd
Housecroft, Catherine E.
b63e2e1e-5ab0-4c20-858f-102cd71e5128
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Palivan, Cornelia G.
75393280-eae2-4ea3-a417-e185970ee139
Price, Jason R.
b4b3362d-8a02-4446-8e83-302ae792f6b0
Zampese, Jennifer A.
0114ba0f-5329-43a4-b991-ab68e15adee9

Constable, Edwin C., Decurtins, Silvio, Housecroft, Catherine E., Keene, Tony D., Palivan, Cornelia G., Price, Jason R. and Zampese, Jennifer A. (2010) Half a grid is better than no grid: competition between 2,2?:6?,2??-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(ii). Dalton Transactions, 39 (9), 2337-2343. (doi:10.1039/b923729a). (PMID:20162207)

Record type: Article

Abstract

The reaction between Cu(NO(3))(2)center dot 3H(2)O, 2,2':6',2 ''-terpyridine(tpy) and 3,6-di(pyrid-2-yl) pyridazine (1) in a 2 : 2 : 1 molar equivalent ratio in aqueous MeCN in the presence of excess NH(4)PF(6) leads to competition between the assembly of the dinuclear half-grid [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O and the mononuclear complex [Cu(1)(2)(OH(2))][PF(6)](2). The yield of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O has been optimized using microwave conditions. [Cu(1)2(OH(2))][PF(6)](2) can be selectively produced by treating Cu(NO(3))(2)center dot 3H(2)O with 1 (1:2 molar equivalents) in aqueous MeCN in the presence of NH(4)PF(6). The single crystal structures of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 4MeNO(2) and [Cu(1)(2)(OH(2))][PF(6)](2) are presented. In the [Cu(2)(1)(tpy)(2)](4+) cation, ligand 1 bridges the two copper(II) centres, each of which is further coordinated by a tpy ligand. The copper(II) coordination geometry is closely associated with the arrangement of the two tpy ligands which engage in efficient face-to-face p-stacking. Magnetic data for crystalline [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 4MeNO(2) are consistent with a weak antiferromagnetic interaction between the two copper(II) centres. EPR spectroscopic data for a powder sample of [Cu(2)(1)(tpy)(2)][PF(6)](4)center dot 2H(2)O are consistent with the dinuclear structure, but in frozen DMF and DMSO solutions, the data indicate that the dinuclear structure of [Cu(2)(1)(tpy)(2)](4+) is not preserved.

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More information

Published date: 19 January 2010
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 351386
URI: http://eprints.soton.ac.uk/id/eprint/351386
ISSN: 0300-9246
PURE UUID: ba4f1755-fad8-4995-81b0-afa569605610
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 22 Apr 2013 10:31
Last modified: 03 Dec 2019 01:36

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