Reactions of [NBU4][Re(O)Cl-4] with bis(pyrazol-1-yl) methane (bpzm) and bis(pyrazol-1-yl)acetate (Hbpza) and with the lithium salts lithium [bis(3,5-dimethylpyrazol-1-yl)acetate] (Libdmpza) and lithium [bis(3,5-dimethylpyrazol-1-yl)methanesulfonate] (Libdmpzs) produce a series of new compounds containing either a kappa(2)-N,N bidentate pyrazolyl ligand [Re(O)(bpzM)Cl-3 (1), Re(O)(bpzm)(OMe)Cl-2 (2), Re(O)(bpzaOMe)(OMe)Cl-2 (4)] or a kappa(3)-N,N,O heteroscorpionate [Re(O)(bpza)Cl-2 (3), Re(O)(bdmpza)Cl-2 isomers 5 and 6, Re(O)(bdmpza)(OMe)Cl (7), Re(O)(bdmpza)(OEt)Cl (8), Re(O)(bdmpzs)(OMe)Cl (9), Re(O)(bdmpzs)(OEt)Cl (10)]. X-ray analyses of 1 and 3 show in both cases a distorted octahedral environment around the rhenium atom. The nature and the geometry of the products are strongly determined by the reaction solvent and by the heteroscorpionate ligand itself. When scorpionates bear methylated pyrazolyl rings mixed heterocomplexes Re(O) (bdmpza) (glycol) (11) and Re(O)(bdmpzs)(glycol) (12) are obtained (H(2)glycol = ethylene glycol). Also 11 shows an octahedral geometry as assessed by X-ray study.