Deprotection, tethering, and activation of a catalytically active metalloporphyrin to a chemically active metal surface: [SAc](4)P-Mn(III)Cl on Ag(100).
The adsorption and subsequent thermal chemistry of the acetyl-protected manganese porphyrin, [SAc](4)P-Mn(III)Cl on Ag(100) have been studied by high resolution XPS and temperature-programmed desorption. The deprotection event, leading to formation of the covalently bound thioporphyrin, has been characterized and the conditions necessary for removal of the axial chlorine ligand have been determined, thus establishing a methodology for creating tethered activated species that could serve as catalytic sites for delicate oxidation reactions. Surface-mediated acetyl deprotection occurs at 298 K, at which temperature porphyrin diffusion is limited. At temperatures above approximately 425 K porphyrin desorption, diffusion and deprotection occur and at >470 K the axial chlorine is removed.
Turner
Mark
M
Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
Vaughan
Owain P H
OP
Kyriakou
Georgios
G
Watson
David J
DJ
Scherer
Lukas J
LJ
Davidson
Greg J E
GJ
Sanders
Jeremy K M
JK
Lambert
Richard M
RM
D000107:Acetylation; D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D013438:Sulfhydryl Compounds / Q000737:chemistry
D008665:Metalloporphyrins; D013438:Sulfhydryl Compounds; D008345:Manganese; D006046:Gold