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


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), 4909-4917. (doi:10.1021/ic800230p).

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Original Publication URL: http://dx.doi.org/10.1021/ic800230p

Description/Abstract

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.

Item Type: Article
ISSNs: 0020-1669 (print)
Related URLs:
Keywords: intrastrand cross-link, anticancer drug cisplatin, crystal-structure, conformer, ligands, dna adducts, duplex dna, head-to-head, retro models, atropisomerization
Subjects: Q Science
Q Science > QD Chemistry
Divisions: University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 54464
Date Deposited: 19 Aug 2008
Last Modified: 27 Mar 2014 18:37
URI: http://eprints.soton.ac.uk/id/eprint/54464

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