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Several rhenium(V) oxo complexes with tetradentate N[sub 2]O[sub 2] Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu[sub 4]][ReOCl[sub 4]] with a tetradentate Schiff base ligand (L[sub 1] = N,N'-ethylenebis(acetylacetoneimine), (acac[sub 2]en) or L[sub 2] = N,N'-propylenebis(acetylacetoneimine) (acac[sub 2]pn))in ethanol solution to generate complexes of the form trans-ReOX(L) where X = CI[sup -], MeO[sup -], ReO[sub 4, sup -], or H[sub 2]O. The product isolated from the reaction was found to be dependent on the reaction conditions, in particular the presence or absence of water and/or base. The μ-oxo-Re[sub 2]O[sub 3](L)[sub 2] dimers were synthesized and characterized for chemical and structural comparison to the related monomers. Conversion of the monomer to its dimer analogue was followed qualitatively by spectrophotometry. The complexes were characterized by ¹H and [sup 13]C NMR, UV-vis, and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. The crystallographic data reported for the structures are as follows: trans-[ReO(OH[sub 2])(acac[sub 2]en)]Cl (H[sub 20]C[sub 12]CIN[sub 2]O[sub 4]Re) 1, triclinic (P&1macr;), a = 7.2888(6) Å, b = 9.8299(8) Å, c = 10.8195(9) Å, α = 81.7670(10)°, β = 77.1510(10)°, γ= 87.6200(10)°, V= 747.96(11), ˚³, Z = 2; trans-[ReO(OReO[sub 3])(acac[sub 2]en)] (H[sub 18]C[sub 12]N[sub 2]O[sub 7]Re[sub 2]) 2, monoclinic (P2[sub 1]/c), a = 7.5547(4) Å, b = 8.7409(5) ,Å, c = 25.7794(13) Å, β = 92.7780(10)°, V = 1700.34(16) ų, Z = 4; trans-[ReOCl(acac[sub 2]pn)] (H[sub 20]C[sub 13]N[sub 2]O[sub 3]CIRe) 3, monoclinic (P2[sub 1]/c), a = 8.1628(5) Å, b = 13.0699(8) Å, c = 28.3902(17) Å, β = 97.5630(10)°, V=3002.5(3) ų, Z=8; trans-[ReO(OMe)(acac[sub 2]pn)] (H[sub 23]C[sub 14]N[sub 2]O[sub 4]Re) 4, monoclinic (P2[sub 1]/c), a = 6.7104(8) Å,, b = 27.844(3) Å, c = 8.2292(9) Å, β = 92.197(2)°, V = 1536.4(3) ų, Z = 4; trans-[μ-oxo-Re[sub 2]O[sub 3](acac[sub 2]en)[sub 2]] (H[sub 36]C[sub 24]N[sub 4]0[sub 7]Re[sub 2]) 5, monoclinic (P2[sub 1]/n), a = 9.0064(5) Å, b = 12.2612(7) Å, c = 12.3695(7) Å, β = 90.2853(10)°, V = 1365.94(13) ų, Z=2; and trans-[μ-oxo Re[sub 2]O[sub 3](acac[sub 2]pn)[sub 2]] (H[sub 40]C[sub 26]N[sub 4]O[sub 7]Re[sub 2]) 6, monoclinic (P2[sub 1]/n), a = 9.1190(5) Å,, b = 12.2452- (7) Å, c = 12.8863(8) Å, β = 92.0510(10)°, V=1438.01(14) ų, Z= 2. [ABSTRACT FROM AUTHOR]