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

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.

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 Creators:
Pantazis, Dimitrios A.1, Author              
McGrady, John E.1, Author
Lynam, Jason M.1, Author
Russell, Christopher A.2, Author
Green, Michael2, Author
Affiliations:
1Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K., ou_persistent22              
2Department of Chemistry, University of Bristol, Cantock's Close, Bristol, UK , ou_persistent22              

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 Abstract: 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.

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Language(s): eng - English
 Dates: 2004-03-302004-06-082004
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/B405609D
 Degree: -

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Title: Dalton Transactions
  Abbreviation : Dalton Trans.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: (14) Sequence Number: - Start / End Page: 2080 - 2086 Identifier: ISSN: 1477-9226
CoNE: https://pure.mpg.de/cone/journals/resource/954925269323