Treatment of NiCl2(dme) and NiBr2(dme) (dme = dimethoxyethane) with 2 equiv of LiOR (OR = (OCBu2Ph)-Bu-t) forms the distorted trigonal planar complexes [NiLiX(OR)(2)(THF)(2)] (THF = tetrahydrofuran) 5 (X = Cl) and 6 (X = Br). The reaction of CuX2 (X = Cl, Br) with 2 equiv of LiOR affords the Cu(I) product Cu-4(OR)(4) (7). The same product can be obtained using the Cu(I) starting material CuCl. NMR studies indicated that the reduction of Cu(II) to Cu(I) is accompanied by the oxidation of the alkoxide RO- to form the alkoxy radical RO center dot, which subsequently forms tert-butyl phenyl ketone by beta-scission. Treatment of compounds 1-4 ([M2Li2Cl2(OR)(4)], M = Cr-Co) with thallium hexafluorophosphate allowed the isolation of the distorted tetrahedral complexes of the form M(OR)(2)(THF)(2) for M = Mn (8), Fe (9), and Co (10). Cyclic voltammetry performed on compounds 8-10 demonstrated irreversible oxidations for all complexes, with the iron complex 9 being the most reducing. Complex 9 shows a reactivity toward PhIO and Ph3SbS to form the corresponding dinuclear iron(III) complexes Fe-2(O)(OR)(4)(THF)(2) (11) and Fe-2(S)(OR)(4)(THF)(2) (12), respectively. X-ray structural studies were performed, showing that the Fe-O-Fe angle for complex 11 is 176.4(1)degrees and that the Fe-S-Fe angle for complex 12 is 164.83(3)degrees.