| Abstract
| - The synthesis and catalytic reactivity of a variety of newruthenium complexes of thetris(pyrazolyl)borate ligand (HB(pz)3) arereported in this paper. From the parent complexRu(HB(pz)3)(COD)X (X = Cl, Br) thecationic derivatives[Ru(HB(pz)3)(COD)L]+ (L =H2O,CH3CN, pyridine, dmso) have been obtained by treatmentwith 1 equiv of AgCF3SO3 inCH2Cl2 solutions of L. Displacement of COD from theselatter complexes has been accomplishedin boiling dmf solutions of ligands L2 =Ph2PCH2PPh2 (dppm),Ph2PCH2CH2NMe2(pn), andMe2NCH2CH2NMe2(tmeda) as well as L = pyridine and 3-methylpyridine to giveRu(HB(pz)3)(L2)Cl andRu(HB(pz)3)(L)2Cl, respectively, each inhigh yield. From some of thesecomplexes, in turn, the chloride ion has been abstracted with eitherAgCF3SO3,TlCF3SO3,or NaBPh4 in CH3CN as the solvent. Inthis way we obtained[Ru(HB(pz)3)(dppm)(CH3CN)]CF3SO3,[Ru(HB(pz)3)(pn)(CH3CN)]BPh4,and[Ru(HB(pz)3)(tmeda)(CH3CN)]BPh4.Selected X-ray structures are included. Some of the complexessynthesized are efficientcatalysts for the formation of selectively C−O-coupled products fromthe reaction ofphenylacetylene with either benzoic acid or allyl alcohols.
- The cationic complexes[Ru(HB(pz)3)(COD)L]+ (L =H2O, CH3CN, pyridine, dmso) have beenobtained by treatment of Ru(HB(pz)3)(COD)X(X = Cl, Br) with 1 equiv of AgCF3SO3 inCH2Cl2 solutions of L. Displacementof COD from these latter complexes has been accomplished in boiling dmfsolutions of ligands L2 =Ph2PCH2PPh2 (dppm),Ph2PCH2CH2NMe2(pn), andMe2NCH2CH2NMe2(tmeda) as well as L = pyridine and 3-methylpyridine to giveRu(HB(pz)3)(L2)Cl andRu(HB(pz)3)(L)2Cl, respectively. Someof the complexes synthesized are efficient catalysts for the formationof selectively C−O-coupled products from the reaction ofphenylacetylene with either benzoic acid or allylalcohols.
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