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NMR and X-ray structural characterization of a cisplatin analogue able to slow down the Pt-N7 rotation of a coordinated guanine base by a billion-fold times: 2,2 '-bipiperidine(dimethylmalonato)platinum(II) complex

Record type: Article

The synthesis and the NMR and X-ray structural characterization of a cisplatin analogue designed to reduce the Pt?N7 rotation of a coordinated guanine base by a billion times are reported. The [Pt(dmm){()-bip}] (dmm = dimethylmalonato; bip = 2,2?-bipiperidine) complex crystallizes in the C2/m space group, which contemplates a mirror plane bisecting the bip and dmm ligands. Because the bip moiety (R,R or S,S configuration at the 2,2?-carbon atoms) does not have planes of symmetry, the requirements of the crystal symmetry are satisfied by a statistical disorder made of bip molecules of R,R or S,S configurations alternating at the same crystallographic site. Such an unexpected arrangement has been permitted by a “quasi planarity” of the bip ligand [maximum deviation from the mean plane through the C and N atoms of 0.2927(9) Å], which allows bip molecules of different chiralities to fit in the same space. The bip array of heavy atoms is overlaid, from both sides, by a layer of “quasi axial” (C)H and (N)H atoms (six per side). Those on one side are hydrogen-bonded to the dmm oxygen atoms of another complex molecule joined in a pair. The distance between the average platinum coordination planes is as short as 3.498(1) Å, comparable to those found in crystals of the [PtCl2(bipy)] complex (bipy = 2,2?-bipyridine) and of graphite, in which, however, all atoms of each unit are rigorously coplanar and there are no out-of-plane hydrogen atoms. The NMR data show a net chemical shift separation between geminal methylene protons, with the “quasi axial” protons being always at higher field with respect to the “quasi equatorial” ones. This is in accordance with a rigid bip ligand frame and the inability of the bip methylene protons adjacent to the coordinated nitrogen to rotate away from a cis-G base (G = guanine) during G rotation around the Pt?N7 bond.

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Citation

Intini, Francesco P., Cini, Renzo, Tamasi, Gabriella, Hursthouse, Michael B. and Natile, Giovanni (2008) NMR and X-ray structural characterization of a cisplatin analogue able to slow down the Pt-N7 rotation of a coordinated guanine base by a billion-fold times: 2,2 '-bipiperidine(dimethylmalonato)platinum(II) complex Inorganic Chemistry, 47, (11), pp. 4909-4917. (doi:10.1021/ic800230p).

More information

Published date: 30 April 2008
Keywords: intrastrand cross-link, anticancer drug cisplatin, crystal-structure, conformer, ligands, dna adducts, duplex dna, head-to-head, retro models, atropisomerization

Identifiers

Local EPrints ID: 54464
URI: http://eprints.soton.ac.uk/id/eprint/54464
ISSN: 0020-1669
PURE UUID: 4d1b43e7-9eb3-4319-ba71-1edf403fc89c

Catalogue record

Date deposited: 19 Aug 2008
Last modified: 17 Jul 2017 14:35

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Contributors

Author: Francesco P. Intini
Author: Renzo Cini
Author: Gabriella Tamasi
Author: Giovanni Natile

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