Manganese(I)-Based Corms With 5-Substituted 3-(2-Pyridyl)Pyrazole Ligands

The reaction of [(OC)(5)MnBr] with substituted 3-(2-pyridyl)pyrazoles) 2-PyPz(R)H (1a-l) in methanol or diethyl ether yields the yellow to orange manganese(I) complexes [(OC)(3)Mn(Br)(2-PyPz(R)H)] (2a-l), the substituents R being phenyl (a), 1-naphthyl (b), 2-anthracenyl (c), 1-pyrenyl (d), 4-bromophenyl (e), 3-bromophenyl (f), duryl (g), 2-pyridyl (h), 2-furanyl (i), 2-thienyl (j), ferrocenyl (k), and 1-adamantyl (l). The carbonyl ligands are arranged facially, leading to three chemically different CO ligands due to different trans-positioned Lewis donors. The diversity of the substituent R demonstrates that this photoCORM backbone can easily be varied with a negligible influence on the central (OC)(3)MnBr fragment, because the structural parameters and the spectroscopic data of this unit are very similar for all these derivatives. Even the ferrocenyl complex 2k shows a redox potential for the ferrocenyl subunit which is identical to the value of the free 5-ferrocenyl-3-(2-pyridyl)pyrazole (1k). The ease of variation of the starting 5-substituted 3-(2-pyridyl)pyrazoles) offers a modular system to attach diverse substituents at the periphery of the photoCORM complex.