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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 8
BKCSDE 32(8)
August 20, 2011 

 
Title
Palladium(II) Aryloxides of Pd(2,6-(CH2NMe2)2C6H3)(OC6H4-X-p) (X = Me, NO2): Synthesis, Property and Reactivity towards Diphenyliodium Chloride
Author
Hyun Sang Jung, Yun Sik Park, Jung Min Seul, Jong Sook Kim, Ho Jin Lee, Soonheum Park *
Keywords
Pd(II) aryloxides, NCN-pincer complex, σ-Ligand exchange, C-O Bond formation
Abstract
para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)(OC6H4-p-X) (NCN = 2,6- (CH2NMe2)2C6H3; X = NO2 (1), Me (2)) were prepared by the reaction of Pd(NCN)(OSO2CF3) with equi-molar amount of NaOC6H4-p-X. Treatment of Pd(NCN)(OSO2CF3) with an excess amount of NaOC6H4-p-Me affords the hydrogen-bonding adduct complex 3 (2·HOC6H4-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free HOC6H4-p-Me. Complex 1 does not undergo adduct formation with HOC6H4-p-NO2 neither from metathesis reaction of Pd(NCN)(OSO2CF3) with an excess amount of NaOC6H4-p-NO2 nor from treatment of 1 with free HOC6H4-p-NO2. Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes σ-ligand exchange reaction with HOC6H4-p-NO2 to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective pKa values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product PhOC6H4-p-Me which was identified by GC/MS spectroscopy.
Page
2711 - 2716
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