Journal Title
Title of Journal: J Chem Sci
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Abbravation: Journal of Chemical Sciences
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Publisher
Springer-Verlag
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Authors: PIYALI PAUL SAMARESH BHATTACHARYA
Publish Date: 2013/01/06
Volume: 124, Issue: 6, Pages: 1165-1173
Abstract
Reaction of a group of Narylpicolinamides picR with RuPPh32CO2Cl2 in refluxing 2methoxyethanol in the presence of a base affords hydrido complexes of two types 1R and 2R which are geometric isomers Similar reaction with Nnaphthylpicolinamide picnap yields an organoruthenium complex 3 via formation of a hydrido intermediate Reaction of 2arylazophenols apR with IrPPh33Cl in refluxing ethanol affords a monohydrido intermediate 4R a dihydrido intermediate 5R and an organoiridium complex 6R as the final product where the azoligand is coordinated as CNOdonor Reaction of apR ligands with RhPPh33Cl yields organorhodium complexes 7R analogous to 6R but without any hydrido intermediate N2′hydroxyphenylbenzaldimines hpbzR react with RhPPh33Cl to yield a group of organorhodium complexes 8R where the hpbzR ligands are coordinated in CNOfashion Upon interaction with IrPPh33Cl 22′6′dimethylphenylazo4methylphenol dmap undergoes a methyl C–H activation and affords organoiridium complex 9 while 22′methylphenylazo4methylphenol mmap undergoes a phenyl C–H activation and gives organoiridium complex 10 Reaction of benzaldehyde thiosemicarbazones bztscR with PdPPh32Cl2 carried out with the expectation of inducing CNSmode of coordination actually has yielded complexes 11R where the bztscR is coordinated in an uncommon NSmode forming a fivemembered chelate ring associated with a restricted rotation around the imine C=N bond These palladium complexes are found to catalyse C–C cross coupling reactions very efficiently Crystal structures of selected complexes of each type have been determined by Xray crystallographyIf an alkyl or aryl C–H bond of a judiciously chosen ligand is brought in close proximity to a platinum metalbound hydride or chloride by coordination through regular donor atoms as in I then facile activation of that C–H bond takes place leading to the formation of cyclometallated species II
Keywords:
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