Help Privacy Policy Disclaimer
  Advanced SearchBrowse




Journal Article

Structure and bonding in the isoelectronic series CnHnP5−n+: is phosphorus a carbon copy?

There are no MPG-Authors in the publication available
External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available

Pantazis, D. A., McGrady, J. E., Lynam, J. M., Russell, C. A., & Green, M. (2004). Structure and bonding in the isoelectronic series CnHnP5−n+: is phosphorus a carbon copy? Dalton Transactions, (14), 2080-2086. doi:10.1039/B405609D.

Cite as: https://hdl.handle.net/21.11116/0000-0007-2ECC-1
The relative stabilities of different isomers of the isoelectronic series CnHnP5−n+ have been investigated using G3X theory. The results indicate that all species containing one or more phosphorus atom adopt a three-dimensional nido geometry, in marked contrast to the planar structure favoured by the all-carbon analogue. Within isomeric nido clusters, a strong correlation between total energy and the nucleus-independent chemical shift (NICS) indicates that three-dimensional aromaticity plays a significant role in determining the stability of the cluster. In the context of these nido clusters, the extent to which phosphorus is a carbon copy proves to be highly dependent on the global electronic environment. The first isolobal substitution of CH by P causes a complete switch from localised to delocalised bonding, accompanied by a transition from a two- to a three-dimensional structure, with the phosphorus atom showing a strong preference for the unique apical site. In contrast, further increasing the phosphorus content causes no further change in structure or bonding, suggesting that, at the basal sites, phosphorus is a rather better carbon copy. The low-energy pathways for interconversion of apical and basal atoms previously identified in C2H2P3+ prove to be a general feature of all members of the series.