ISSN:
0749-1581
Keywords:
13C NMR
;
195P Pt NMR
;
(4-X-thiophenolato) (2,2′:6′,24-terpyridine)platinum(II) complexes
;
Substituent effects
;
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A series of (4-X-thiophenolato) (2,2′:6′,2″-terpyridine)platinum(H) complexes [X = H, F, Cl, Br, CH3, OCH3, NH2, N(CH3)2, NO2, COOCH3, CN, NH3+], which have potential as DNA intercalators, have been synthesized. 13C and 195Pt NMR spectra of these complexes have been obtained in both D2O and DMSO-d6. The 195Pt shifts are highly sensitive to both solvent and distant substituent effects and span a chemical shift range of 72 ppm. The propagation and transmission of substituent effects within the complexes have been studied, and the 195Pt and thiophenolato C-1 13C chemical shifts correlated with Hammett substituent constants, using the dual substituent approach. The results show that the (terpy)Pt - S - group is an effective π-donor to the aromatic ring. Further, a normal substituent chemical shift effect is seen with the thiophenol C-1, whereby electron-withdrawing groups cause a decrease in electron density, whereas the platinum centre shows the reverse effect, i.e. electron-withdrawing groups cause an increase in electron density. The latter effect has been explained in terms of a π-polarization effect, with electron density from the terpyridine ligand being supplied to the platinum centre in response to demand by the thiophenol substituent.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1260250607
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