Deprotection, Tethering, and Activation of a Catalytically Active Metalloporphyrin to a Chemically Active Metal Surface: [SAc]4P−Mn(III)Cl on Ag(100)

• Published in: Journal of the American Chemical Society Vol. 131; no. 5; pp. 1910 - 1914
• Main Authors: Turner, Mark, Vaughan, Owain P. H, Kyriakou, Georgios, Watson, David J, Scherer, Lukas J, Davidson, Greg J. E, Sanders, Jeremy K. M, Lambert, Richard M
• Format: Journal Article
• Language: English
• Published: American Chemical Society 11.02.2009
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja8076389

The adsorption and subsequent thermal chemistry of the acetyl-protected manganese porphyrin, [SAc]4P−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 ∼425 K porphyrin desorption, diffusion and deprotection occur and at >470 K the axial chlorine is removed.