Photochemistry of group 8 metal complexes of type [M(bpy)2 cyanogen] (M = iron, ruthenium). Photosynthesis of heteroleptic iron(II) compounds and photoionization of ruthenium(II) compounds, or, Photoassisted synthesis of heteroleptic iron(II) compounds and photoionization of ruthenium(II) complexes.

摘要

[Fe(bpy)2(CN)2] was shown to undergo photoinduced replacement of cyano ligands with various bidentate ligands to generate heteroleptic iron(II) complexes. Complexes of type [Fe(bpy)2(NCCH3) 2]2+ and [Fe(bpy)2(L)]2+ (L = bpy, Me2bpy, en, dppn) were synthesized by photochemical means with a quantum yields of 0.016 +/- 0.002. The proposed synthesis more convenient than the typical "one pot" reactions that have many undesired byproducts and tedious separation and purification steps after the reaction. The heteroleptic iron(II) complexes may now be produced in high yields and new complexes could be synthesized for various studies, including DNA interactions.;[Ru(bpy)2(CN)2 was shown to reduce halogenated solvents from its excited state using high energy irradiation. There is an energy/electron transfer between Ru2+ and Ru3+ accounting for changes in the 1H-NMR spectrum. Thermal reversion of the Ru3+ complex back to the Ru2+ system after being heated in a 60°C water bath occurred after 5 minutes. This photochemistry represents a viable method to break down and dispose of halogenated solvents. The quantum yield for photoionization of [Ru(bpy) 2(CN)2] was 0.057 +/- 0.002.