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An unexpected substitution of the anionic chelating ligands at the M II centre by a neutral tripodal ligand has been observed in the reaction of Mn II , Co II , Ni II and Cu II hexafluoroacetylacetonates (hfac) with tris(2-pyridyl)phosphine (Py 3 P) or its oxide (Py 3 P = O). The nature of the metal ion in M(hfac) 2 and the M/L ratio determine the degree of substitution of hfac-anions (partial vs. total) and therefore, the structure of the complex formed (scorpionate vs. bis-scorpionate ones, respectively). Hence, the reaction of the ligands with [Cu(hfac) 2 (H 2 O) 2 ] in an equimolar ratio affords scorpionate [Cu(N,N',N''-Py 3 P = X)(O,O'-hfac)(O-hfac)], wherein one hfac-ligand chelates metal, while the other hfac acts as an O-monodentate one. Using the two equivalents of Py 3 P in this reaction leads to [Cu(N,N',N''-Py 3 P) 2 ](hfac) 2 , which contains a bis-scorpionate cation [Cu(Py 3 P) 2 ] 2+ and two noncoordinated hfac-anions. [Co(hfac) 2 (H 2 O) 2 ] and [Ni(hfac) 2 (H 2 O) 2 ], regardless of the M/L molar ratio, react with Py 3 P = O to give cationic scorpionates [M(N,N',N''-Py 3 P = O)(O,O'-hfac)(H 2 O)](hfac), in which one hfac-anion is noncoordinated. In contrast, [Mn(hfac) 2 (H 2 O) 2 ], on interaction with Py 3 P, results in the cationic complex [Mn(N,N',N''-Py 3 P) 2 ][Mn(hfac) 3 ] 2 bearing a bis-scorpionate cation [Mn(Py 3 P) 2 ] 2+ and two [Mn(hfac) 3 ] 2  - counterions. The synthesized scorpionates have been characterized by X-ray diffractometry, cyclic voltammetry, SQUID magnetometry, FT-IR and UV-Vis techniques.

dalton transactions

Variable coordination of tris(2-pyridyl)phosphine and its oxide toward M(hfac)<sub>2</sub>: a metal-specifiable switching between the formation of mono- and bis-scorpionate complexes

Variable coordination of tris(2-pyridyl)phosphine and its oxide toward M(hfac)2: a metal-specifiable switching between the formation of mono- and bis-scorpionate complexes

Variable coordination of tris(2-pyridyl)phosphine and its oxide toward M(hfac)₂: a metal-specifiable switching between the formation of mono- and bis-scorpionate complexes