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Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts

Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts
Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts
We have demonstrated that treatment of [Fe(1)(2)](2+) (1 = 4'-(4-pyridyl)-2,2':6',2 ''-terpyridine) with an excess of CuCl(2)center dot 2H(2)O leads to competition between coordination of copper(II) by the pendant pyridine donors in [Fe(1)(2)](2+), and transfer of ligand 1 from iron(II) to copper(II) to yield [{Cl(3)Cu(mu-1)Fe(mu-1)}(2)CuCl(2)(OH(2))(2)]Cl(2)center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4H(2)O, respectively. Direct reaction of 1 with CuCl(2)center dot 2H(2)O and variation in crystallization conditions results in the formation of either monomeric or polymeric complexes: [Cu(1)Cl(2)]center dot 4.75H(2)O, [Cu(1)Cl(2)]center dot H(2)O center dot MeOH and [Cu(1)Cl(2)center dot 2H(2)O](n). The reaction of 1 with Cu(NO(3))(2)center dot 3H(2)O gives the coordination polymer [Cu(1)(ONO(2))(2)center dot H(2)O](n). Magnetic data for [Cu(1)Cl(2)center dot 2H(2)O](n) and [Cu(1)(ONO(2))(2)center dot H(2)O](n) are consistent with antiferromagnetically- coupled chains. Reactions of CuCl(2)center dot 2H(2)O with ligands 2 and 3 (2 = 4'-(3-pyridyl)-2,2':6',2 ''-terpyridine, 3 = 4'-(2-pyridyl)-2,2':6',2 ''-terpyridine) lead to monomeric complexes. With the exception of [Cu(3)Cl(2)], the mononuclear complexes show a propensity for the incorporation of water into their crystal lattices; in the case of [Cu(H1)Cl(2)]Cl center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4.75H(2)O, the small change in water content leads to the assembly of (5.8(2))(2)(5.6.8)(4)(5(2).6)(2) or (4(2).6(2))(3)(4.6(2))(6) water-chloride ion nets.
1466-8033
2406-2416
Beves, Jonathon E.
354e102b-5b63-4f9b-9519-5ae5d99ac7c3
Constable, Edwin C.
d7da4205-ec75-47b5-a666-9ce90618069b
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd
Dunphy, Emma L.
6b44255a-ffdf-4c26-879d-da1e25f78540
Housecroft, Catherine E.
b63e2e1e-5ab0-4c20-858f-102cd71e5128
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Neuburger, Markus
332bf835-af5c-4431-a39c-f280d04783ea
Schaffner, Silvia
3f252531-0710-41ad-aa93-1282573d2a2a
Zampese, Jennifer A.
0114ba0f-5329-43a4-b991-ab68e15adee9
Beves, Jonathon E.
354e102b-5b63-4f9b-9519-5ae5d99ac7c3
Constable, Edwin C.
d7da4205-ec75-47b5-a666-9ce90618069b
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd
Dunphy, Emma L.
6b44255a-ffdf-4c26-879d-da1e25f78540
Housecroft, Catherine E.
b63e2e1e-5ab0-4c20-858f-102cd71e5128
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Neuburger, Markus
332bf835-af5c-4431-a39c-f280d04783ea
Schaffner, Silvia
3f252531-0710-41ad-aa93-1282573d2a2a
Zampese, Jennifer A.
0114ba0f-5329-43a4-b991-ab68e15adee9

Beves, Jonathon E., Constable, Edwin C., Decurtins, Silvio, Dunphy, Emma L., Housecroft, Catherine E., Keene, Tony D., Neuburger, Markus, Schaffner, Silvia and Zampese, Jennifer A. (2009) Structural diversity in the reactions of 4?-(pyridyl)-2,2?:6?,2?-terpyridine ligands and bis{4?-(4-pyridyl)-2,2?:6?,2?-terpyridine}iron(II) with copper(II) salts. CrystEngComm, 11 (11), 2406-2416. (doi:10.1039/b909639f).

Record type: Article

Abstract

We have demonstrated that treatment of [Fe(1)(2)](2+) (1 = 4'-(4-pyridyl)-2,2':6',2 ''-terpyridine) with an excess of CuCl(2)center dot 2H(2)O leads to competition between coordination of copper(II) by the pendant pyridine donors in [Fe(1)(2)](2+), and transfer of ligand 1 from iron(II) to copper(II) to yield [{Cl(3)Cu(mu-1)Fe(mu-1)}(2)CuCl(2)(OH(2))(2)]Cl(2)center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4H(2)O, respectively. Direct reaction of 1 with CuCl(2)center dot 2H(2)O and variation in crystallization conditions results in the formation of either monomeric or polymeric complexes: [Cu(1)Cl(2)]center dot 4.75H(2)O, [Cu(1)Cl(2)]center dot H(2)O center dot MeOH and [Cu(1)Cl(2)center dot 2H(2)O](n). The reaction of 1 with Cu(NO(3))(2)center dot 3H(2)O gives the coordination polymer [Cu(1)(ONO(2))(2)center dot H(2)O](n). Magnetic data for [Cu(1)Cl(2)center dot 2H(2)O](n) and [Cu(1)(ONO(2))(2)center dot H(2)O](n) are consistent with antiferromagnetically- coupled chains. Reactions of CuCl(2)center dot 2H(2)O with ligands 2 and 3 (2 = 4'-(3-pyridyl)-2,2':6',2 ''-terpyridine, 3 = 4'-(2-pyridyl)-2,2':6',2 ''-terpyridine) lead to monomeric complexes. With the exception of [Cu(3)Cl(2)], the mononuclear complexes show a propensity for the incorporation of water into their crystal lattices; in the case of [Cu(H1)Cl(2)]Cl center dot 4H(2)O and [Cu(H1)Cl(2)]Cl center dot 4.75H(2)O, the small change in water content leads to the assembly of (5.8(2))(2)(5.6.8)(4)(5(2).6)(2) or (4(2).6(2))(3)(4.6(2))(6) water-chloride ion nets.

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More information

Published date: 27 July 2009
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 351387
URI: https://eprints.soton.ac.uk/id/eprint/351387
ISSN: 1466-8033
PURE UUID: 483cb440-c818-4f29-a03e-2c1f39b1cae0
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 22 Apr 2013 10:19
Last modified: 29 Oct 2019 01:38

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