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| - Oxidation of Ruthenium(II) to Ruthenium(IV) η4-DieneComplexes: Swing Mechanism and Diene−AllylConversion
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| - This paper reports on the synthesis and reactivity of Ru(IV)η4-diene complexes of thetypeRu(η5-C5Me5)(η4-diene)Br2+obtained by oxidative bromine additions to Ru(II)η4-dienecomplexes. Mechanistic details are derived from the reactionproducts varying with theoxidizing agent and the leaving ligand and are backed up by extendedHückel molecularorbital calculations. The diene fragment in Ru(IV) is proneto gauche deformation and istherefore extremely susceptible to nucleophilic attack of even weakanionic bases generatingthe corresponding Ru(IV) η3-allyl complexes.Accordingly, Ru(IV) η4-diene complexesarestabilized either by using 2,3-disubstituted diene ligands in whichcase gauche deformationis highly unfavorable or else by excluding nucleophilic agents.For the latter method, twoconvenient routes to affording Ru(IV) η4-dienecomplexes are (i) the reaction ofBr+CF3SO3-withRu(η5-C5Me5)(η4-diene)Brand (ii) the reaction of dibromine with labileRu(η5-C5Me5)(η4-diene)(CF3SO3). The conversion of theRu(II) η4-diene to the Ru(IV)η4-diene complex issuggested to proceed via a swing of the diene ligand by changing thedihedral angle betweenthe C5Me5 and diene ligands from about+20 to about −70° concomitantly pushing the leavingligand (Br- orCF3SO3-) out.
- This paper reports on thesynthesis and reactivity of Ru(IV) η4-dienecomplexes of the type[Ru(η5-C5Me5)(η4-diene)Br2]+obtained by oxidative bromine additions to Ru(II)η4-diene complexes. Mechanistic details are derivedfrom the reaction products varying with the oxidizing agent and theleaving ligand and are backed up by extended Hückel molecularorbital calculations.
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