Abstract: Abstract: Copper(I) complexes with fluorinated alkoxide ligands with the form K[Cu(OCRMe F2 )2 ], in which R = MeF ( 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 {Cun O 2 }species were observed. Manometric O2 uptake studies showed dinuclear {Cu2 O2 } and triuclear {Cu3 O 2 } 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 18 O 2 confirmed O2 as the source of the ligand hydroxyl O atom. A tetrameric Cu(II) carbonate complex, {{K2 (DME)1.5 }[Cu(OCMeMe F2 )2 CO3 ]}4 (14 ), was obtained from CO2 addition to the {Cu2 O3 } 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(OCRMeF2 ) 2 ] complexes are retained in solution. Ionic copper(I) complexes of the form {K(18C6)}[Cu(OCRMeF2 )2 ] in which R = MeF (7 ), Ph (8 ), or Me ( 9 ) and (Ph4 P)[Cu(OCRMeF2 ) 2 ], with R = MeF (10 ) were prepared, none of which react with O2 at -78°C. The Cu(II) alkoxide compounds {K(18C6)}[Cu(OCRMeF 2 )3 ], in which R= MeF (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 = H2 O (17 ) or DME (18 ). Diamagnetic Zn(II) derivatives with aryloxide ligands of the form {K(18C6)} 2 [Zn(OAr)4 ], in which Ar = ArF (19 ) or Ar' (20 ) and {K(18C6)}[Zn(OCRMeF2 ) 3 ], with R = Ph (21 ) were also prepared and characterized by X-ray crystallography and multinuclear NMR.