Formation of Pd 2X 2(μ-S)(μ-dpm) 2 by reaction of PdX 2(dpm) with H 2S in the presence of alumina (X=halogen, dpm=diphenylphosphinomethane)

• Published in: Journal of molecular catalysis. A, Chemical Vol. 139; no. 2; pp. 159 - 169
• Main Authors: Wong, Terrance Y.H., James, Brian R., Wong, Philip C., Mitchell, Keith A.R.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 1999
• Subjects: Alumina; H 2S; Pd 2X 2(μ-S)(μ-dpm) 2; PdX 2(dpm); Pd 2X 2(μ-S)(μ-dpm) 2; PdX 2(dpm); H 2S; Alumina
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/S1381-1169(98)00201-5

Alumina promotes the reaction of PdX 2(dpm) ( 3) (X=Cl, Br, I) with H 2S to form Pd 2X 2(μ-S)(dpm) 2 ( 2) 1 For convenience, μ-dpm in 2 is written simply as dpm. 1 and HX, with chemisorption of the HX (quantified by titration) providing the driving force; although no intermediate species are detected, the reaction likely proceeds via mercapto species formed via `alumina activated H 2S'. XPS studies show interactions of species 2 and 3 with alumina, these interactions being weak as demonstrated by recovery of the species on dissolution using an appropriate solvent. For the iodide system, adsorbed HI on alumina undergoes partial photodecomposition to give I 2 and H atoms.