Novel rhenium(V) oxo complexes containing bis(pyrazol-1-yl)acetate and bis(pyrazol-1-yl) sulfonate as tripodal N,N,O-heteroscorpionate ligands

Marina Porchia; Grazia Papini; Carlo Santini; Giancarlo Gioia Lobbia; Maura Pellei; Francesco Tisato; Giuliano Bandoli; Alessandro Dolmella

doi:10.1021/ic050193x

Novel rhenium(V) oxo complexes containing bis(pyrazol-1-yl)acetate and bis(pyrazol-1-yl) sulfonate as tripodal N,N,O-heteroscorpionate ligands

Inorg Chem. 2005 May 30;44(11):4045-54. doi: 10.1021/ic050193x.

Authors

Marina Porchia¹, Grazia Papini, Carlo Santini, Giancarlo Gioia Lobbia, Maura Pellei, Francesco Tisato, Giuliano Bandoli, Alessandro Dolmella

Affiliation

¹ Department of Chemical Sciences, University of Camerino, Via S. Agostino 1, 62032 Camerino (MC), Italy. [email protected]

PMID: 15907134
DOI: 10.1021/ic050193x

Abstract

Reactions of [NBu4][Re(O)Cl4] 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 kappa2-N,N bidentate pyrazolyl ligand [Re(O)(bpzm)Cl3 (1), Re(O)(bpzm)(OMe)Cl2 (2), Re(O)(bpzaOMe)(OMe)Cl2 (4)] or a kappa3-N,N,O heteroscorpionate [Re(O)(bpza)Cl2 (3), Re(O)(bdmpza)Cl2 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 (H2glycol = ethylene glycol). Also 11 shows an octahedral geometry as assessed by X-ray study.