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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...
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Published in: | Dalton transactions : an international journal of inorganic chemistry 2017-05, Vol.46 (18), p.5965-5975 |
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Main Authors: | , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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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. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c7dt00339k |