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Coordination properties of unsymmetrical Schiff base ligands containing N3 donor sets when restricted to bidentate chelate bonding modes. Crystal structures of fac-[PtIMe3(PMAMP)] (PMAMP=2-{(2?-pyridylmethylene)aminomethyl}pyridine) and fac-[PtIMe3(PMAQ)] (PMAQ=8-{(2?-pyridylmethylene)amino}quinoline)

Coordination properties of unsymmetrical Schiff base ligands containing N3 donor sets when restricted to bidentate chelate bonding modes. Crystal structures of fac-[PtIMe3(PMAMP)] (PMAMP=2-{(2?-pyridylmethylene)aminomethyl}pyridine) and fac-[PtIMe3(PMAQ)] (PMAQ=8-{(2?-pyridylmethylene)amino}quinoline)
Coordination properties of unsymmetrical Schiff base ligands containing N3 donor sets when restricted to bidentate chelate bonding modes. Crystal structures of fac-[PtIMe3(PMAMP)] (PMAMP=2-{(2?-pyridylmethylene)aminomethyl}pyridine) and fac-[PtIMe3(PMAQ)] (PMAQ=8-{(2?-pyridylmethylene)amino}quinoline)
The N3 ligands 2-{(2?-pyridylmethylene)aminomethyl}pyridine, (PMAMP), 8-{(2?-pyridylmethylene)amino}quinoline, (PMAQ) and 2-[{(6?-methyl-2?-pyridyl)methylene}aminomethyl]pyridine (MPMAMP) are analogous to 2,2?:6?,2?-terpyridine in respect of their spatial arrangement of N donor atoms. When acting as bidentate chelates PMAMP and PMAQ bind exclusively to the PtIV moiety PtIMe3 such that the five-membered chelate rings incorporate the imine bond. This was deduced by detailed solution NMR studies and X-ray crystal structures. In contrast, the ligand MPMAMP, with 6-methyl substitution of the pyridyl ring attached to the carbon of the imine bond, preferentially, but not exclusively, coordinates to the nitrogen of the other pyridyl ring. The population ratio of the two complexes formed was 6:1 (303 K, CDCl3 solution), but there was no NMR evidence of exchange between these species, in the temperature range 303–413 K, resulting from 1,4-metallotropic shifts, as occurs in analogous complexes such as fac-[PtIMe3(2,2?:6?,2?-terpyridine)].
platinum(iv) complexes, unsymmetrical schiff base ligands, x-ray structures, nmr spectratransition-metal complexes, nuclear-magnetic-resonance, tricarbonylhalide-complexes, 2, 6-bispyridine, fluxionality, m=pd
0020-1693
209-220
Creber, M. L.
71d2ca9d-7d07-4571-a634-7afcb7c1ac0c
Orrell, K. G.
e291cfb7-374a-4a7f-8e30-d9513f5203c4
Osborne, A. G.
9430fd91-c186-4b98-a713-74d9b6fbba4b
Sik, V.
ce381a83-89b1-4d4c-82b0-57a0c143dd36
Coles, S. J.
503a9d9c-0380-4fcd-ad31-cd329255c08e
Hibbs, D. E.
bcaa2c3a-d480-46a7-b65a-50b8ee172f73
Hursthouse, M. B.
276e7125-0773-43f6-97e3-77106e9b6e8f
Creber, M. L.
71d2ca9d-7d07-4571-a634-7afcb7c1ac0c
Orrell, K. G.
e291cfb7-374a-4a7f-8e30-d9513f5203c4
Osborne, A. G.
9430fd91-c186-4b98-a713-74d9b6fbba4b
Sik, V.
ce381a83-89b1-4d4c-82b0-57a0c143dd36
Coles, S. J.
503a9d9c-0380-4fcd-ad31-cd329255c08e
Hibbs, D. E.
bcaa2c3a-d480-46a7-b65a-50b8ee172f73
Hursthouse, M. B.
276e7125-0773-43f6-97e3-77106e9b6e8f

Creber, M. L., Orrell, K. G., Osborne, A. G., Sik, V., Coles, S. J., Hibbs, D. E. and Hursthouse, M. B. (2000) Coordination properties of unsymmetrical Schiff base ligands containing N3 donor sets when restricted to bidentate chelate bonding modes. Crystal structures of fac-[PtIMe3(PMAMP)] (PMAMP=2-{(2?-pyridylmethylene)aminomethyl}pyridine) and fac-[PtIMe3(PMAQ)] (PMAQ=8-{(2?-pyridylmethylene)amino}quinoline). Inorganica Chimica Acta, 299 (2), 209-220. (doi:10.1016/S0020-1693(99)00500-9).

Record type: Article

Abstract

The N3 ligands 2-{(2?-pyridylmethylene)aminomethyl}pyridine, (PMAMP), 8-{(2?-pyridylmethylene)amino}quinoline, (PMAQ) and 2-[{(6?-methyl-2?-pyridyl)methylene}aminomethyl]pyridine (MPMAMP) are analogous to 2,2?:6?,2?-terpyridine in respect of their spatial arrangement of N donor atoms. When acting as bidentate chelates PMAMP and PMAQ bind exclusively to the PtIV moiety PtIMe3 such that the five-membered chelate rings incorporate the imine bond. This was deduced by detailed solution NMR studies and X-ray crystal structures. In contrast, the ligand MPMAMP, with 6-methyl substitution of the pyridyl ring attached to the carbon of the imine bond, preferentially, but not exclusively, coordinates to the nitrogen of the other pyridyl ring. The population ratio of the two complexes formed was 6:1 (303 K, CDCl3 solution), but there was no NMR evidence of exchange between these species, in the temperature range 303–413 K, resulting from 1,4-metallotropic shifts, as occurs in analogous complexes such as fac-[PtIMe3(2,2?:6?,2?-terpyridine)].

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More information

Published date: 15 March 2000
Keywords: platinum(iv) complexes, unsymmetrical schiff base ligands, x-ray structures, nmr spectratransition-metal complexes, nuclear-magnetic-resonance, tricarbonylhalide-complexes, 2, 6-bispyridine, fluxionality, m=pd

Identifiers

Local EPrints ID: 19051
URI: https://eprints.soton.ac.uk/id/eprint/19051
ISSN: 0020-1693
PURE UUID: 19f48ba8-234c-4af7-92d7-b2370fa9b30e

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Date deposited: 03 Jan 2006
Last modified: 17 Jul 2017 16:34

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