Polycarbonyl

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Polycarbonyl, (also known as polymeric-CO, p-CO or poly-CO) is a solid, metastable, and explosive polymer of carbon monoxide. [1] The polymer is produced by exposing carbon monoxide to high pressures. The structure of the solid appears amorphous, but may include a zigzag of equally-spaced CO groups. [2]

Contents

Formation

Poly-CO can be produced at pressures of 5.2 GPa; it is amorphous and yellow to dark red in color. [3] Polymerisation is catalysed by blue light at slightly lower pressures in the δ-phase of solid CO. [4] Another white, crystalline phase can be made at higher temperatures at 6 or 7 GPa. [1]

R. J. Mills discovered this solid, which was first produced in a tungsten carbide anvil in 1947. Originally this was thought to be polymeric carbon suboxide, but the formation does not yield any gas byproduct such as carbon dioxide. [5] The yield of the solid can be up to 95%. [6]

Properties

The polymer is stable above about 80 K. Below this temperature the ε form of solid molecular CO is formed instead. When the pressure is released the polymer remains stable at atmospheric pressure. The solid dissolves in water, alcohol and acetone. [5] When exposed to the atmosphere it is hygroscopic, becomes gluey, and changes colour, becoming darker. [6] The reaction with water produces carboxylic groups. [7] [8]

The solid stores a high energy. It can decompose explosively forming glassy carbon and carbon dioxide. [6] The energy density stored can be up to 8 kJ/g. During the decomposition the temperature can be 2500 K. [6] The density is 1.65 g/cm3, however most of the solid produced is porous, so the true density is likely to be higher. [6]

Infrared spectroscopy shows bands at 650, 1210, 1440, 1650 and 1760 cm−1. The 1760 band is likely to be due to the -C-(C=O)-C- structure. [4] The 1600 is due to vibration of a C=C double bond. [6]

The solid is electrically insulating with an electronic gap energy of 1.9 eV. [4]

Nuclear magnetic resonance for the material made from 13CO shows sharp resonance at 223 ppm due to ester or lactone attached carbon, and 151 ppm due to C=C double bonds. There is also broad resonance at 109 and 189 ppm. Over time of a few days, the 223 ppm peak reduces and all the other features increase in strength. [6]

Structure

Ideas of the structure include a zigzag chain of CO pointing in opposite directions, or five atom rings connected by CO and C−C bonds. The rings are lactones of tetronic acid: −C:−(C=O)−(C−O)−(C=O)−O−. Interconnections between the rings are zigzags of CO. [4]

Other ideas of the structure of the solid, include graphitic carbon with carbon dioxide under pressure, and a polymer with this C3O2 monomer: −(C=O)−O−(C)=C<. Yet other ideas are that the solid is the same as the polymer of carbon suboxide with oxalic anhydride. [9]

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or [–C(CH
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n
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with loss of water. It can also be prepared by ring-opening polymerization of lactide [–C(CH
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)HC(=O)O–]
2
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References

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  2. Podeszwa, Rafał; Rodney J. Bartlett (2003). "Crystal orbital study of polycarbonyl". International Journal of Quantum Chemistry. 95 (4–5): 638–642. doi:10.1002/qua.10655. ISSN   0020-7608.
  3. Rademacher, Nadine; Lkhamsuren Bayarjargal; Wolfgang Morgenroth; Jennifer Ciezak-Jenkins; Sasha Batyrev; Björn Winkler. "High Pressure Investigations of Liquid and Polymerized CO up to 20 GPa Using Pair Distribution Function Analysis" (PDF). Retrieved 30 May 2013.
  4. 1 2 3 4 Bernard, Stephane (Feb 1998). "DECOMPOSITION AND POLYMERIZATION OF SOLID CARBON MONOXIDE UNDER PRESSURE" (PDF). Trieste. Retrieved 30 May 2013.
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  6. 1 2 3 4 5 6 7 Lipp, Magnus J.; William J. Evans, Bruce J. Baer, Choong-Shik Yoo; Baer, Bruce J.; Yoo, Choong-Shik (2005). "High-energy-density extended CO solid" (PDF). Nature Materials. 4 (3): 211–215. Bibcode:2005NatMa...4..211L. doi:10.1038/nmat1321. ISSN   1476-1122. PMID   15711555. S2CID   25779399.{{cite journal}}: CS1 maint: multiple names: authors list (link)
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  9. Lipp, M.; W. J. Evans; V. Garcia-Baonza; H. E. Lorenzana (1998). "Carbon Monoxide: Spectroscopic Characterization of the High–Pressure Polymerized Phase". Journal of Low Temperature Physics. 111 (3/4): 247–256. Bibcode:1998JLTP..111..247L. doi:10.1023/A:1022267115640. ISSN   0022-2291. S2CID   116687814.

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