Heterotrimetallic paramagnetic complex of ring reduced tin() hexadecachlorophthalocyanine
Coordination complex (Cp* 2 Cr III ) + {CpFe II (CO) 2 (Sn II [PcCl 16 ] 4− )} − ( 1 ) has been obtained by the reduction of tin( iv ) dichloride hexadecachlorophthalocyanine (PcCl 16 ) by decamethylchromocene (Cp* 2 Cr) in the presence of {CpFe I (CO) 2 } 2 . The process is accompanied by oxidation...
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Published in: | New journal of chemistry 2023-04, Vol.47 (14), p.6924-6931 |
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Main Authors: | , , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
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Summary: | Coordination complex (Cp*
2
Cr
III
)
+
{CpFe
II
(CO)
2
(Sn
II
[PcCl
16
]
4−
)}
−
(
1
) has been obtained by the reduction of tin(
iv
) dichloride hexadecachlorophthalocyanine (PcCl
16
) by decamethylchromocene (Cp*
2
Cr) in the presence of {CpFe
I
(CO)
2
}
2
. The process is accompanied by oxidation of Cr
II
and Fe
I
centers and the formation of paramagnetic Cr
III
and diamagnetic Fe
II
species. Two-electron reduction of a macrocycle and the formation of diamagnetic [PcCl
16
]
4−
as well as a transition of tin(
iv
) to tin(
ii
) occur. The [PcCl
16
]
4−
tetraanions are formed in (cryptand(K
+
))
2
{Sn
IV
Cl
2
[PcCl
16
]
4−
}
2−
·2C
6
H
4
Cl
2
(
2
) obtained by the reduction of Sn
IV
PcCl
16
by mild reductant - fullerene C
60
&z.rad;
−
radical anions. Complexes
1
and
2
precipitate as crystals. Sandwich-type assemblies are formed in
1
. Two (Cp*
2
Cr
III
)
+
cations are sandwiched between two {CpFe
II
(CO)
2
(Sn
II
[PcCl
16
]
4−
)}
−
planes, whereas layers of the {Sn
IV
Cl
2
[PcCl
16
]
4−
}
2−
macrocycles are formed in
2
. The formation of the [PcCl
16
]
4−
tetraanions in both
1
and
2
is supported by the data of structural analysis, optical spectroscopy and magnetic measurements. Susceptibility measurements correspond to the contribution of one non-interacting Cr
III
spin (
S
= 3/2) per formula unit. Weak antiferromagnetic coupling is observed between the spins. Only Cr
III
atoms contribute to EPR spectra of
1
, whereas salt
2
is diamagnetic and EPR silent.
The crystalline paramagnetic complex based on ring-reduced tin(
ii
) hexadecachlorophthalocyanine has been obtained and characterized. Two paramagnetic (Cp*
2
Cr
III
)
+
cations are sandwiched between the diamagnetic {CpFe
II
(CO)
2
(Sn
II
[PcCl
16
]
4−
)}
−
anions. |
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ISSN: | 1144-0546 1369-9261 |
DOI: | 10.1039/d3nj00506b |