Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

Dipti Patel, Jonathan McMaster, William Lewis, Alexander J. Blake and Stephen T. Liddle ()
Additional contact information
Dipti Patel: School of Chemistry, University of Nottingham, University Park
Jonathan McMaster: School of Chemistry, University of Nottingham, University Park
William Lewis: School of Chemistry, University of Nottingham, University Park
Alexander J. Blake: School of Chemistry, University of Nottingham, University Park
Stephen T. Liddle: School of Chemistry, University of Nottingham, University Park

Nature Communications, 2013, vol. 4, issue 1, 1-8

Abstract: Abstract Despite the abundance of f-block–cyclopentadienyl, arene, cycloheptatrienyl and cyclo-octatetraenide complexes, cyclobutadienyl derivatives are unknown in spite of their prevalence in the d-block. Here we report that reductive [2+2]-cycloaddition reactions of diphenylacetylene and (2,2-dimethylpropylidyne)phosphine with uranium(V)-inverted sandwich 10π-toluene tetra-anion complexes results in the isolation of inverted sandwich cyclobutadienyl and diphosphacyclobutadienyl dianion uranium(IV) complexes. Computational analysis suggests that the bonding is predominantly electrostatic. Although the ψ4 molecular orbital in the cyclobutadienyl and diphosphacyclobutadienyl ligands exhibits the correct symmetry for δ-bonding to uranium, the dominant covalent contributions arise from π-bonding involving ψ2 and ψ3 orbital combinations. This contrasts with uranium complexes of larger arenes and cyclo-octatetraenide, where δ-bonding dominates. This suggests that the angular requirements for uranium to bond to a small four-membered ring favours π-bonding, utilizing 5f- instead of 6d-orbitals, over δ-bonding that is favoured with larger ligands, where 6d-orbitals can become involved in the bonding.

Date: 2013
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/ncomms3323 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:4:y:2013:i:1:d:10.1038_ncomms3323

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/ncomms3323

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().