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All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer

All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer
All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer
The role of ligand basicity in complex formation has been investigated using monodentate pyridines or benzimidazole (M) in combination with a solution-stable species derived form a coordination polymer, [Cu(L)] (where L = 2-(2-hydroxybenzylidene-amino)phenol). The 12 [Cu(L)(M)n] complexes generated, combined with the [Cu(L)]2(P) complexes from our previous work (where P is a polypyridyl ligand), allow us to gauge the likelihood of complex formation based on the pKa of the conjugate acid of the pyridyl ligands and Hammett parameter, σ. Above pKa ≈ 4.5, complexes are formed where the only ligands are L2− and M or P and the packing interactions are predominantly van der Waals. Below this value, complex formation is unlikely unless there additional oxygen ligands in the d_(z^2 ) of the Cu(II) ion. The structures of two literature [Cu(L)(B)] complexes, where B is a chelating bidentate pyridyl ligand are also re-examined to resolve the disorder in the [Cu(L)] moiety.
0300-9246
Beddoe, Samuel, Vladimir Forbes
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Lonergan, Rhona F.
cafcb2e2-00ca-4eef-87ab-81eecfa659bf
Pitak, Mateusz
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Price, Jason R.
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Coles, Simon J.
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Kitchen, Jonathan A
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Keene, Tony
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Beddoe, Samuel, Vladimir Forbes
f029ab1b-b5ad-4c0c-9243-fbf876f5bbe6
Lonergan, Rhona F.
cafcb2e2-00ca-4eef-87ab-81eecfa659bf
Pitak, Mateusz
eeb6a00f-2291-4376-830f-d30dfd607ed1
Price, Jason R.
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Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Kitchen, Jonathan A
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Keene, Tony
fb859c26-6a1d-4c43-a15f-f329bc8d34d7

Beddoe, Samuel, Vladimir Forbes, Lonergan, Rhona F., Pitak, Mateusz, Price, Jason R., Coles, Simon J., Kitchen, Jonathan A and Keene, Tony (2019) All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer. Dalton Transactions. (doi:10.1039/C9DT01527B).

Record type: Article

Abstract

The role of ligand basicity in complex formation has been investigated using monodentate pyridines or benzimidazole (M) in combination with a solution-stable species derived form a coordination polymer, [Cu(L)] (where L = 2-(2-hydroxybenzylidene-amino)phenol). The 12 [Cu(L)(M)n] complexes generated, combined with the [Cu(L)]2(P) complexes from our previous work (where P is a polypyridyl ligand), allow us to gauge the likelihood of complex formation based on the pKa of the conjugate acid of the pyridyl ligands and Hammett parameter, σ. Above pKa ≈ 4.5, complexes are formed where the only ligands are L2− and M or P and the packing interactions are predominantly van der Waals. Below this value, complex formation is unlikely unless there additional oxygen ligands in the d_(z^2 ) of the Cu(II) ion. The structures of two literature [Cu(L)(B)] complexes, where B is a chelating bidentate pyridyl ligand are also re-examined to resolve the disorder in the [Cu(L)] moiety.

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Keene 2019 CEC paper - Accepted Manuscript
Restricted to Repository staff only until 22 July 2020.
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Accepted/In Press date: 16 July 2019
e-pub ahead of print date: 22 July 2019

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Local EPrints ID: 434054
URI: https://eprints.soton.ac.uk/id/eprint/434054
ISSN: 0300-9246
PURE UUID: c5698842-9b0f-433a-b20d-075e3ca7943b
ORCID for Mateusz Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Jonathan A Kitchen: ORCID iD orcid.org/0000-0002-7139-5666
ORCID for Tony Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 11 Sep 2019 16:30
Last modified: 12 Sep 2019 00:37

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Contributors

Author: Samuel, Vladimir Forbes Beddoe
Author: Rhona F. Lonergan
Author: Mateusz Pitak ORCID iD
Author: Jason R. Price
Author: Simon J. Coles ORCID iD
Author: Jonathan A Kitchen ORCID iD
Author: Tony Keene ORCID iD

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