Diazirine-modified gold nanoparticle: template for efficient photoinduced interfacial carbene insertion reactions.
Photolysis of a 3-aryl-3-(trifluoromethyl)diazirine-modified monolayer-protected gold nanoparticles (2-C(12)MPNs), with a core size of 1.8 ± 0.3 nm, in the presence of model carbene trapping reagents leads to efficient, essentially quantitative, modification of the interface via carbene insertion reactions. The utility of carbene insertion reactions as a general approach for the modification of Au-MPNs to provide a breadth of new structures available was demonstrated using acetic acid, methanol, benzyl alcohol, phenol, benzylamine, methyl acrylate, and styrene (10a-g, respectively) as electrophilic carbene trapping agents to form the corresponding modified 3a-g-C(12)MPNs. The 1.8 ± 0.3 nm gold nanoparticles bearing a diazirine group (2-C(12)MPNs) were synthesized using the ligand exchange reaction with the requisite 3-aryl-3-(trifluoromethyl)diazirinealkylthiol. The 2-C(12)MPNs and the resulting products of the reaction on the MPN (3a-g-C(12)MPN) were fully characterized by IR, (1)H NMR, and (19)F NMR spectroscopy and, when applicable, transmission electron microscopy (TEM). Verification for the 3a-g-C(12)MPNs was accomplished by comparison of the spectral data to those of obtained for the photoreactions of 3-(3-methoxyphenyl)-3-(trifluoromethyl)-3H-diazirine as a model with 10a-g.
Ismaili
Hossein
H
Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7.
Lee
Soo
S
Workentin
Mark S
MS
D000475:Alkenes / Q000737:chemistry; D003978:Diazomethane / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D053768:Metal Nanoparticles / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D010782:Photolysis
D000475:Alkenes; D008024:Ligands; C030011:carbene; D003978:Diazomethane; D006046:Gold; D008697:Methane