Mechanistic study of the synthesis of CdSe nanocrystals: release of selenium.
We outline a reaction pathway for the cleavage of the P═Se bond in trialkylphosphine selenide during the synthesis of CdSe nanocrystals. The reaction between cadmium carboxylate and trimethylphosphine selenide in the presence of an alcohol produces alkoxytrimethylphosphonium (2). Control experiments and density functional theory calculations suggested that the cleavage of the P═Se bond is initiated by nucleophilic attack of carboxylate on a Cd(2+)-activated phosphine selenide to produce an acyloxytrialkylphosphonium intermediate (1), which is converted to 2 in the presence of an alcohol.
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Raúl
R
García-Rodríguez
Haitao
H
Liu
D019187:Cadmium Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D010720:Phosphines / Q000737:chemistry; D011789:Quantum Theory; D018036:Selenium Compounds / Q000737:chemistry*
D019187:Cadmium Compounds; D002264:Carboxylic Acids; D010720:Phosphines; D018036:Selenium Compounds; C049750:trimethyl phosphine; C058667:cadmium selenide