Ligand substitution reactions of some sterically hindered Pt(II) complexes. The crystal structures of [TLp>tp>p>Bup>Hb>2b>](ClOb>4b>)b>2b>路0.5Hb>2b>O

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• 作者：Mirjana 膼urovi膰p>ap> ; Jovana Bogojeskip>ap> ; Biljana Petrovi膰p>ap> ; Dejan Petrovi膰p>bp> ; Frank W. Heinemannp>cp> ; 沤ivadin D. Bugar膷i膰p>ap>p> ; p>p>bugarcic@kg.ac.rsp>
• 关键词：TLtBu ; 2 ; 6-bis[(1 ; 3-di-tert-butylimidazolin-2-imino)methyl]pyridine ; tpdm ; terpyridinedimethane
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：28 June, 2012
• 卷：41
• 期：1
• 页码：70-76
• 文件大小：642 K

摘要

Substitution reactions of the complexes [(TLp>tp>p>Bup>)PtCl]p>+p> and [Pt(tpdm)Cl]p>+p>, where TLp>tp>p>Bup> = 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine and tpdm = terpyridinedimethane, with nucleophiles: thiourea, Ip>鈭?/sup>, Brp>鈭?/sup>, NOb>2b>p>鈭?/sup>, pyridine and dimethyl-sulfoxide (DMSO) were studied in 0.1 M NaClOb>4b> aqueous solution in the presence of 10 mM NaCl. The reactions were carried out at three different temperatures (288, 298 and 308 K) using variable-temperature UV-VIS spectrophotometer. The substitutions were followed under the pseudo-first-order conditions with a large excess of nucleophiles. The slightly higher reactivity of complex with tpdm ligand can be attributed to the influence of the bulkiness of tert-butyl-groups from [(TLp>tp>p>Bup>)PtCl]p>+p> complex. The order of reactivity of studied ligands is: thiourea > Ip>鈭?/sup> > Brp>鈭?/sup> > NOb>2b>p>鈭?/sup> > pyridine > DMSO. The negative values reported for entropy of activation confirmed the associative substitution mode. These results are discussed in order to find the connection between structure and reactivity of the complexes with tridentate sterically hindered ligands. The crystal structure of [TLp>tp>p>Bup>Hb>2b>](ClOb>4b>)b>2b>路0.5Hb>2b>O was determined by X-ray diffraction.