1. Dioxygen reactivity of multinuclear fluorinated copper(I) alkoxides facilitated by secondary ligand interactions 2. synthesis and characterization of monomeric O-donor complexes of divalent copper and zinc

Abstract

Thesis (Ph.D.)--Boston University PLEASE NOTE: Boston University Libraries did not receive an Authorization To Manage form for this thesis or dissertation. It is therefore not openly accessible, though it may be available by request. If you are the author or principal advisor of this work and would like to request open access for it, please contact us at [email protected]. Thank you.Copper(I) complexes with fluorinated alkoxide ligands with the form K[Cu(OCRMe^F2)2], in which R = Me^F (4), Ph (5), or Me (6), were synthesized and characterized. The dioxygen (O2) reactivity of the series of complexes was investigated at -78°C and two stoichiometries of {CunO2} species were observed. Manometric O2 uptake studies showed dinuclear {Cu2O2} and triuclear {Cu3O2} species and their chromophores were measured with UV-vis spectroscopy. Warming these species to room temperature resulted in irreversible spectroscopic changes, and ligand hydroxylation was observed for complexes 5 and 6. ESI-MS study of reactions with 18O2 confirmed O2 as the source of the ligand hydroxyl O atom. A tetrameric Cu(II) carbonate complex, {{K2(DME)1.5}[Cu(OCMeMe^F2)2C03]}4 (14), was obtained from CO2 addition to the {Cu2O3} moiety derived from 6. Irreversible reduction of O2 required secondary potassium-ligand (K···F and K-O) interactions which bridge multiple [Cu(OCRMe^F2)2]- anions in solid-state structures of 4, 5, and 6, and were quantified by K+ cation bond valence analysis. Solution conductivity studies confirmed that neutral aggregates of K[Cu(OCRMe^F2)2] complexes are retained in solution. Ionic copper(I) complexes of the form {K(18C6)}[Cu(OCRMe^F2)2] in which R = Me^F (7), Ph (8), or Me (9) and (Ph4P)[Cu(OCRMe^F2)2], with R = Me^F (10) were prepared, none of which react with O2 at -78°C. The Cu(II) alkoxide compounds {K(18C6)}[Cu(OCRMe^F2)3], in which R= Me^F (15) and Me (16) were prepared and spectroscopically and magnetically characterized. Compound 16 was demonstrated to be trigonal-planar by X-ray crystallography and all other data for 15 are consistent with trigonal-planar coordination. Two four-coordinate Cu(II) compounds with dodecafluoropinacolate (ddfp) ligands were also synthesized and characterized spectroscopically. The structurally characterized square-planar ddfp compounds have the form {K(solvent)2}2[Cu(ddfp)2], in which solvent= H2O (17) or DME (18). Diamagnetic Zn(II) derivatives with aryloxide ligands of the form {K(18C6)}2[Zn(OAr)4], m which Ar = A^F (19) or Ar' (20) and {K(18C6)}[Zn(OCRMe^F2)3], with R = Ph (21) were also prepared and characterized by X-ray crystallography and multinuclear NMR