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Photochemistry of Group 8 Metal Complexes of Type [M(bpy)2(CN)2] (M = Fe, Ru). Photosynthesis of Heteroleptic Iron(II) Compounds and Photoionization of Ruthenium(II) Compounds

Turner, David Benjamin
http://rave.ohiolink.edu/etdc/view?acc_num=osu1253238745

Abstract Details

2009, Doctor of Philosophy, Ohio State University, Chemistry.
[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 o 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.
Dr. Claudia Turro, PhD (Advisor)
Dr. Sheldon Shore, PhD (Committee Member)
Dr. Patrick Woodward, PhD (Committee Member)
143 p.
Chemistry
Photochemistry; Iron; Ruthenium; Heteroleptic; Photoionization

Recommended Citations

Citations

  • Turner, D. B. (2009). Photochemistry of Group 8 Metal Complexes of Type [M(bpy)2(CN)2] (M = Fe, Ru). Photosynthesis of Heteroleptic Iron(II) Compounds and Photoionization of Ruthenium(II) Compounds [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1253238745

    APA Style (7th edition)

  • Turner, David. Photochemistry of Group 8 Metal Complexes of Type [M(bpy)2(CN)2] (M = Fe, Ru). Photosynthesis of Heteroleptic Iron(II) Compounds and Photoionization of Ruthenium(II) Compounds. 2009. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1253238745.

    MLA Style (8th edition)

  • Turner, David. "Photochemistry of Group 8 Metal Complexes of Type [M(bpy)2(CN)2] (M = Fe, Ru). Photosynthesis of Heteroleptic Iron(II) Compounds and Photoionization of Ruthenium(II) Compounds." Doctoral dissertation, Ohio State University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=osu1253238745

    Chicago Manual of Style (17th edition)

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This open access ETD is published by The Ohio State University and OhioLINK.