Synthesis of new bis(acetylide)-substituted fluorene derivatives and their bimetallic and polymeric complexes

Jack Lewis, Paul R. Raithby, Wai Yeung Wong

Research output: Contribution to journalArticle

96 Citations (Scopus)

Abstract

A new series of bis(acetylide) organic ligands having fluorene or fluorenone moieties in the backbone, 2,7-di(trimethylsilylethynyl)fluorene (1a), 2,7-di(ethynyl)fluorene (1b), 2,7-di(trimethylsilylethynyl)fluoren-9-one (2a) and 2,7-di(ethynyl)fluoren-9-one (2b), has been prepared. Reaction of the diterminal alkynyl fluorene derivatives 1b and 2b with two equivalents of the complex trans-[(Ph)(PEt3)2Pt(Cl)] in CH2Cl2/iPr2NH with catalyic CuI readily affords the diplatinum(II) bis(acetylide) complexes trans-[(Ph)(PEt3)2Pt-CC-R1-CC-Pt(PEt 3)2(Ph)] (R1=2,7-fluorenyl 3) and trans-[(Ph)(PEt3)2Pt-CC-R2-CC-Pt(PEt 3) 2(Ph)] (R2=2,7-fluoren-9-onyl 4) in good yields. Two new rigid-rod organometallic polymers trans-[-Pt(PBun3)2-CC-R1-CC-]∞ (5) and trans-[-Pt(PBun3)2-CC-R2-CC-]∞ (6) have also been prepared in good yields, in a similar manner to their dinuclear complexes 3 and 4, by the CuI-catalysed dehydrohalogenation reaction of trans-[Pt(PBun3)2Cl2] with one equivalent of 1b or 2b, in an amine solvent, at ambient temperature. Both poly-yne polymers (colourless 5, deep red 6) exhibit good solubility in common organic solvents and readily cast into thin films. The organometallic terminal alkyne complexes trans-[Cl(dppm)2M-CC-R2-CCH] (M=Ru 7, Os 8), obtained by treatment of 2b with one equivalent of cis-[M(dppm)2Cl2] (M=Ru, Os), based on a NaPF6/DBU method have been utilised as starting products for access to the homobimetallic trans-[Cl(dppm)2M-CC-R2-CC-M(dppm)2Cl] (M=Ru 9, Os 10) and heterobimetallic trans-[Cl(dppm)2Ru-CC-R2-CC-Os(dppm)2Cl] (11) systems by reaction with a suitable choice of cis-M(dppm)2Cl2 (M=Ru or Os). All the new compounds have been characterised by analytical and spectroscopic methods, and the single-crystal X-ray structure of 1b has been determined.

Original languageEnglish
Pages (from-to)219-228
Number of pages10
JournalJournal of Organometallic Chemistry
Volume556
Issue number1-2
DOIs
Publication statusPublished - 15 Apr 1998

Keywords

  • Acetylide
  • Fluorenyl ligand
  • Osmium
  • Platinum
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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