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New arene ruthenium complexes with planar chirality
Date de parution
2004
In
Inorganica Chimica Acta, Elsevier, 2004/357/1/219-224
Résumé
1,2,4-Trimethyl-cyclohexadiene reacts with RuCl<sub>3</sub> • <i>n</i>H<sub>2</sub>O in refluxing ethanol to afford quantitatively [RuCl<sub>2</sub>(1,2,4-C<sub>6</sub>H<sub>3</sub>Me<sub>3</sub>)]<sub>2</sub> (<b>1</b>), the coordination of 1,2,4-trimethylbenzene to the ruthenium atom introducing planar chirality at the η<sup>6</sup>-arene ligand. The dinuclear complex <b>1</b> reacts with two equivalents of triphenylphosphine (PPh<sub>3</sub>) to give quantitatively, as a racemic mixture of enantiomers, [RuCl<sub>2</sub>(1,2,4-C<sub>6</sub>H<sub>3</sub>Me<sub>3</sub>)(PPh<sub>3</sub>)] (<b>2</b>), the structure of which has been determined by a single-crystal X-ray structure analysis of (rac)-2. Similarly, 1 reacts with two equivalents of the enantiopure phosphine (1S,2S,5R)-(+)-neomenthyldiphenylphosphine (nmdpp) to afford in good yield [RuCl<sub>2</sub>(1,2,4-C6H<sub>3</sub>Me<sub>3</sub>)(nmdpp)] (<b>3</b>) as a mixture of diastereoisomers, from which the isomer <b>3a</b> was isolated by crystallisation. A single-crystal X-ray structure analysis of <b>3a</b> allowed the determination of the absolute configuration at the planar chiral <sup>η</sup>6-arene moiety. Finally, complex 1 reacts with one equivalent of the diphosphine ligand 1,1′-bis(diphenylphosphino)ferrocene (dppfc) to give the heteronuclear complex [RuCl<sub>2</sub>(1,2,4-C<sub>6</sub>H<sub>3</sub>Me<sub>3</sub>) (dppfc)RuCl2(1,2,4-C<sub>6</sub>H<sub>3</sub>Me<sub>3</sub>)] (<b>4</b>). All complexes were fully characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopies.
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Type de publication
journal article
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