Much improved synthetic procedures for ReOCl4, ReO3Cl, ReOMe4, Li2, and ReMe6 are described.Interaction of ReOCl4 with methanol in the presence of amine gives the unusual alkoxo-compound (MeO)2ORe(μ-O)(μ-OMe)2ReO(OMe)2, (A), while LiOBut gives ReO(OBut)4, and LiOPri gives an unusual dimeric species i)5>*LiCl(thf)2>2, (B) (thf = tetrahydrofuran).The interaction with phenol in the presence of trimethylphosphine leads to the compound trans-Re(OPh)4(PMe3)2, (C) while with lithium bis(trimethylsilyl)-amide a unique four-co-ordinate rhenium(V) compound, ReO3, is obtained.The crystal and molecular structures of (A)-(C) have been determined by X-ray crystallography.Compound (A) is monoclinic, space group P21/n, a = 12.142(1), b = 15.369(1), c = 7.311(1) Angstroem, β = 90.22(1)deg, and Z = 4.Compound (B) is triclinic, space group P1, a = 14.602(5), b = 13.363(3), c = 9.244(6) Angstroem, α = 98.39(4), β = 102.35(5), γ = 68.71(2)deg, and Z = 1.Compound (C) is monoclinic, space group P21/c, a = 10.079(2), b = 10.527(3), c = 14.443(3) Angstroem, β = 97.28(2) deg, and Z = 2.The structures have been refined to R values of 0.059 (A), 0.069(B)' and 0.055 (C) using respectively 1965, 4061, and 1797 observed intensities, measured on a diffractometer.