Multiple Isomerism (cis/trans; syn/anti) in (dmso)2Pt(aryl)2 Complexes: A Combined Structural, Spectroscopic, and Theoretical Investigation

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Organometallics, 24 (17): 4125--4131 (2005)
DOI: 10.1021/om050076


The occurrence of cis or trans configurations in square planar diarylbis(DMSO)platinum(II) complexes with S-bonded DMSO ligands and aryl = 2,3,4,5,6-pentamethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2-, 3-, and 4-methylphenyl, and Ph has been investigated by multinuclear (1H, 13C, and 195Pt) NMR spectroscopy and crystal structure anal. Both methods confirm the cis configuration for complexes with the smaller Ph and methylphenyl (tolyl) ligands and the trans configuration for the compds. with the bulkier ligands, starting from 2,6-dimethylphenyl. Spectroscopic criteria could thus be established to identify configurational isomers. For the 2-tolyl complex an addnl. kind of isomerism arises from the relative orientation of the two Me substituents on the same side (syn) or on different sides of the coordination plane (anti). 2D-NMR spectroscopy allowed us to identify the conformers and to study isomerization mechanisms. DFT calcn. results agree well with the exptl. structures and with the spectroscopic data. on SciFinder(R)



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