Loading…

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

An unexpected substitution of the anionic chelating ligands at the M centre by a neutral tripodal ligand has been observed in the reaction of Mn , Co , Ni and Cu hexafluoroacetylacetonates (hfac) with tris(2-pyridyl)phosphine (Py P) or its oxide (Py P = O). The nature of the metal ion in M(hfac) and...

Full description

Saved in:
Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2017-05, Vol.46 (18), p.5965-5975
Main Authors: Artem'ev, Alexander V, Kashevskii, Alexey V, Bogomyakov, Artem S, Safronov, Alexander Yu, Sutyrina, Anastasiya O, Telezhkin, Anton A, Sterkhova, Irina V
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:An unexpected substitution of the anionic chelating ligands at the M centre by a neutral tripodal ligand has been observed in the reaction of Mn , Co , Ni and Cu hexafluoroacetylacetonates (hfac) with tris(2-pyridyl)phosphine (Py P) or its oxide (Py P = O). The nature of the metal ion in M(hfac) 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) (H O) ] in an equimolar ratio affords scorpionate [Cu(N,N',N''-Py 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 P in this reaction leads to [Cu(N,N',N''-Py P) ](hfac) , which contains a bis-scorpionate cation [Cu(Py P) ] and two noncoordinated hfac-anions. [Co(hfac) (H O) ] and [Ni(hfac) (H O) ], regardless of the M/L molar ratio, react with Py P = O to give cationic scorpionates [M(N,N',N''-Py P = O)(O,O'-hfac)(H O)](hfac), in which one hfac-anion is noncoordinated. In contrast, [Mn(hfac) (H O) ], on interaction with Py P, results in the cationic complex [Mn(N,N',N''-Py P) ][Mn(hfac) ] bearing a bis-scorpionate cation [Mn(Py P) ] and two [Mn(hfac) ] counterions. The synthesized scorpionates have been characterized by X-ray diffractometry, cyclic voltammetry, SQUID magnetometry, FT-IR and UV-Vis techniques.
ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt00339k