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Uptake of one and two molecules of CO 2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation
Tetrahedral [MoO 4 ] 2− readily binds CO 2 at room temperature to produce a robust monocarbonate complex, [MoO 3 (κ 2 -CO 3 )] 2− , that does not release CO 2 even at modestly elevated temperatures (up to 56 °C in solution and 70 °C in the solid state). In the presence of excess carbon dioxide, a se...
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| Published in: | Chemical science (Cambridge) 2014, Vol.5 (5), p.1772-1776 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Tetrahedral [MoO
4
]
2−
readily binds CO
2
at room temperature to produce a robust monocarbonate complex, [MoO
3
(κ
2
-CO
3
)]
2−
, that does not release CO
2
even at modestly elevated temperatures (up to 56 °C in solution and 70 °C in the solid state). In the presence of excess carbon dioxide, a second molecule of CO
2
binds to afford a pseudo-octahedral dioxo dicarbonate complex, [MoO
2
(κ
2
-CO
3
)
2
]
2−
, the first structurally characterized transition-metal dicarbonate complex derived from CO
2
. The monocarbonate [MoO
3
(κ
2
-CO
3
)]
2−
reacts with triethylsilane in acetonitrile under an atmosphere of CO
2
to produce formate (69% isolated yield) together with silylated molybdate (quantitative conversion to [MoO
3
(OSiEt
3
)]
−
, 50% isolated yield) after 22 hours at 85 °C. This system thus illustrates both the reversible binding of CO
2
by a simple transition-metal oxoanion and the ability of the latter molecular metal oxide to facilitate chemical CO
2
reduction. |
|---|---|
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/C4SC00132J |