Issue 20, 2000

Synthesis, structures and properties of platinum(II) complexes of oligoacetylenic sulfides

Abstract

A series of novel platinum(II) acetylide complexes incorporating sulfur-linked oligoalkynes have been prepared. The CuI-catalysed dehydrohalogenation reactions of the mono-protected dialkyne ligand HC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS) (TIPS = Pri3Si) with trans-[Pt(PBu3)2Cl2], cis-[Pt(dppe)Cl2] or cis-[Pt(Me2bipy)Cl2] (Me2bipy = 4,4′-dimethyl-2,2′-bipyridine), in the presence of a base, readily produced trans-[Pt(PBu3)2{C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS)}2] 1, cis-[Pt(dppe){C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS)}2] 3 and cis-[Pt(Me2bipy){C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS)}2] 7, respectively, in good yields. Similar synthetic procedures using a diacetylenic sulfide species HC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS) afforded trans-[Pt(PBu3)2{C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS)}2] 2 and cis-[Pt(dppe){C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C(TIPS)}2] 4, both of which contain eight triple-bond units within the molecular entity. Two new metallo-end-capped derivatives trans-[Ph(Et3P)2Pt–C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C–Pt(PEt3)2Ph] 5 and trans-[Ph(Et3P)2Pt–C[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]C–Pt(PEt3)2Ph] 6 were also synthesized in moderate yields by reactions of two equivalents of trans-[PtPh(Cl)(PEt3)2] and the diterminal acetylenic sulfides HC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CH and HC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSC[triple bond, length as m-dash]CH in a CuI/(Me3Si)2NH system. All of the compounds 1–7 have been characterized by IR, NMR (1H, 13C and 31P) and UV/VIS spectroscopies, luminescence measurements and mass spectrometry. The solid-state molecular structures of 5 and 7 have been established by X-ray crystallography.

Supplementary files

Article information

Article type
Paper
Submitted
30 May 2000
Accepted
22 Aug 2000
First published
19 Sep 2000

J. Chem. Soc., Dalton Trans., 2000, 3675-3680

Synthesis, structures and properties of platinum(II) complexes of oligoacetylenic sulfides

H. Zhang, A. W. M. Lee, W. Wong and M. S. M. Yuen, J. Chem. Soc., Dalton Trans., 2000, 3675 DOI: 10.1039/B004253F

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