Coordination capacity of Keggin anions as polytopic ligands: case study of [VNbO]
Reaction of Na 9 H 4 [VNb 12 O 40 {NbO(CO 3 )} 2 ] with [(C 6 H 6 )RuCl 2 ] 2 (molar ratio {VNb 12 } : {(C 6 H 6 )Ru} = 1 : 4) in aqueous solution gives a mixture of [α-{(C 6 H 6 )Ru} 4 VNb 12 O 40 ] 7− and [α-{(C 6 H 6 )Ru} 3 VNb 12 O 40 ] 9− . Direct acetone diffusion into mother liquor leads to c...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 5; no. 2; pp. 778 - 784 |
|---|---|
| Main Authors | , , , , , , , |
| Format | Journal Article |
| Published |
28.05.2021
|
| Online Access | Get full text |
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| Summary: | Reaction of Na
9
H
4
[VNb
12
O
40
{NbO(CO
3
)}
2
] with [(C
6
H
6
)RuCl
2
]
2
(molar ratio {VNb
12
} : {(C
6
H
6
)Ru} = 1 : 4) in aqueous solution gives a mixture of [α-{(C
6
H
6
)Ru}
4
VNb
12
O
40
]
7−
and [α-{(C
6
H
6
)Ru}
3
VNb
12
O
40
]
9−
. Direct acetone diffusion into mother liquor leads to crystallization of Na
6
H[α-{(C
6
H
6
)Ru}
4
VNb
12
O
40
]·41.25H
2
O (
1
), characterized by single crystal X-ray diffraction (SCXRD). This anion has four organometallic fragments coordinated to the α-Keggin type [VNb
12
O
40
]
15−
backbone in different manner. Three {(C
6
H
6
)Ru}
2+
groups cap triangular faces and one group a rectangular face of [VNb
12
O
40
]
15−
. Equilibrated mixture of [α-{(C
6
H
6
)Ru}
4
VNb
12
O
40
]
7−
and [α-{(C
6
H
6
)Ru}
3
VNb
12
O
40
]
9−
was studied by
1
H DOSY NMR, HPLC-ICP-AES and HPLC-ESI-MS combined techniques. Direct chromatographic separation of these complexes results in unexpected transformation of both species into [α-{(C
6
H
6
)Ru}
5
VNb
12
O
40
]
5−
, isolated and characterized as Na
5
[α-{(C
6
H
6
)Ru}
5
VNb
12
O
40
]·16H
2
O (
2
). This anion contains five coordinated organometallic groups occupying both triangular and rectangular faces.
[VNb
12
O
40
]
15−
polytopic ligand can coordinate to up to five {(C
6
H
6
)Ru}
2+
groups. Combined analytical separation tools together with
1
H DOSY NMR were firstly applied to the solution studies of polyoxoniobate based complexes. |
|---|---|
| Bibliography: | Electronic supplementary information (ESI) available: Experimental part, SCXRD data, HPLC-ESI-MS, HR-ESI-MS data. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 2068338 10.1039/d1dt00765c 1504795 and |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d1dt00765c |