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• W2071827587 abstract "A series of thiourea dianion complexes [Pt{SC(NPh)NR}(PPh 3 ) 2 ] (R = Me, Et, Pr n , Pr i , Bu n , Bu t and p -tol) was synthesised from cis -[PtCl 2 (PPh 3 ) 2 ] and the asymmetrically disubstituted thioureas PhNHC(S)NHR in the presence of triethylamine base. With the exception of the t -butyl complex, all complexes initially form the distal isomer, with the NR group remote from the platinum centre, and a coordinated NPh group; isomerisation occurs in solution to the thermodynamically more stable proximal isomer with a coordinated NR group. The isomerisation process was investigated by NMR spectroscopy and DFT calculations; the X-ray structure of the proximal isomer of [Pt{SC(=NPh)NEt}(PPh 3 ) 2 ] is also reported. • Series of platinum(II) complexes of asymmetric thiourea dianions synthesised. • Isomerisation process investigated by 1 H and 31 P{ 1 H} NMR spectroscopies. • DFT calculations provide information on relative energies of proximal and distal isomers. • X-ray structure of proximal isomer [Pt{SC(=NPh)NEt}(PPh 3 ) 2 ] is reported. A series of thiourea dianion complexes [Pt{SC(NPh)NR}(PPh 3 ) 2 ] (R = Me, Et, Pr n , Pr i , Bu n , Bu t and p -tol) was synthesised from cis -[PtCl 2 (PPh 3 ) 2 ] and the asymmetrically disubstituted thioureas PhNHC(S)NHR in the presence of triethylamine base. The complexes were studied by 1 H and 31 P{ 1 H} NMR, IR and Raman spectroscopies, and ESI mass spectrometry. In each case, the NMR spectrum of a freshly-prepared CDCl 3 solution shows the presence of an initially formed, kinetically favoured isomer, which then converts to the thermodynamically favoured isomer. For all cases except when R = Bu t , the initial isomer has the R substituent in a distal position, viz. [Pt{SC(=NR)NPh}(PPh 3 ) 2 ], which then isomerises in solution to the thermodynamically favoured proximal isomer [Pt{SC(=NPh)NR}(PPh 3 ) 2 ]. However, when R = Bu t , the thermodynamically-favoured isomer has the distal configuration, [Pt{SC(=NBu t )NPh}(PPh 3 ) 2 ]. DFT-optimised geometries of each isomer allowed the calculation of the difference in Gibbs free energy between the distal and proximal isomers, ΔG(=G dist − G prox ), which is positive for all compounds except R = Bu t . The rate of isomerisation can be qualitatively correlated with the magnitude of ΔG. Trends in the values of ΔG are discussed in terms of substituent steric effects." @default.
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• W2071827587 date "2015-01-01" @default.
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• W2071827587 title "Isomerism in platinum(II) complexes of asymmetrically 1,3-disubstituted thiourea dianion ligands" @default.
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• W2071827587 doi "https://doi.org/10.1016/j.ica.2014.10.019" @default.
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