Near-UV photolysis of mu-dibromotetrabromodipalladate(II) in chloroform

作者：Dilorenzo Kelly K; Gilbert Rachel M; Hoggard Patrick E^*

来源：Journal of Coordination Chemistry, 2010, 63(4): 558-567.

DOI：10.1080/00958970903582696

• Photolysis
• Photosubstitution
• mu-Dibromotetrabromodipalladate(II)
• Photodecomposition
• Chloroform

Broadband (lambda > 320 nm) irradiation of (Bu(4)N)(2)Pd(2)Br(6) in chloroform causes the conversion of Pd(2)Br(6)(2-) to Pd(2)Cl(6)(2-). During the conversion, chloroform is decomposed photocatalytically at a rate that accelerates then decelerates as coordinated bromines are replaced by chlorines. The primary bromine-containing product is CCl(3)Br. The observations are consistent with a mechanism in which Pd(2)Br(6)(2-) and the intermediate Pd(2)Br(6-n)Cl(n)(2-) complexes undergo homolytic photodissociation of a bromine or chlorine atom, which terminates with a trichloromethyl radical or abstracts a hydrogen from chloroform, respectively.

• 出版日期2010