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Crystal Structures of Cobalt Sandwich Complexes in the η5-Cyclopentadienyl/η4-Cyclobutadiene and η5-Cyclopentadienyl/η4-Cyclopentadienone Families

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Abstract

The crystal structures of six cobalt sandwich complexes—four in the η5-cyclopentadienyl/η4-cyclobutadiene family, two from the related η5-cyclopentadienyl/η4-cyclopentadienone family—are presented and discussed alongside related structural precedents. In each of the complexes an undecorated cyclopentadienyl ligand is present whereas the partner cyclobutadiene or cyclopentadienone ligand bears four identical aromatic substituents (phenyl, p-tolyl, p-fluorophenyl, 2-thienyl or 2,2′-bithienyl). This range of substituents allows for detailed structural comparison between members of the families of sandwich complexes presented here, and with previously reported structures.

Graphic Abstract

Crystal structures of members of the η5-cyclopentadienyl/η4-tetraarylcyclobutadiene (left) and η5-cyclopentadienyl/η5-cyclopentadienone (right) families of sandwich complexes are presented.

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Scheme 1
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Notes

  1. One previously reported structure which has been excluded from Table 2 is the (η5–Cp)Co(η4–C4R4) complex where R = 4–(ethoxycarbonyl)phenyl (this structure, CCDC entry NEVCOG, was published alongside NEVCIA and NEVCUM) [20]. The X-ray crystal structure of this material reveals a packing mode in which extended columns of stacked sandwich complexes exhibit fourfold symmetry about a central axis. Furthermore, these stacks contain partial occupancy Co atoms on either side of the rings with occupancies of 79% and 21%. In essence, the sandwich complexes are disordered over two sites within these columns. The measured Co···Cp (centroid) distance for the major fraction is 1.63 Å with a corresponding Co···C4R4 distance of 1.79 Å (with a dihedral angle of 2°). Both of these distances are clearly incomparable with the other structures in Table 2 and provide the reason for exclusion from comparison. It should be noted that it is possible that this type of disorder is also present in the structure of NEVCIA (Co occupancies of 97% and 3%).

  2. For 1–3 ring designations proceed in numerical order as indicated by the labelled carbon attachment points in Figs. 1, 2 and 3; for 4 the individual thiophene rings are paired, 1 with 2 and so forth, according to the labelled sulfur atoms in Fig. 4. The dihedral angles between connected thiophene rings in 4 are also listed.

  3. There exists one other structure worthy of note (DAKJAA) that features a mixed superphane structure of CpCo-capped cyclobutadiene and cyclopentadienone rings [26]. However, the lack of any aryl substituents in this case limits useful comparison with either of the sets of structures in this work.

  4. In addition to variation in thienyl ring orientation with respect to the central cyclopentadienone ring, complex 6 (while presenting two unique molecules in the asymmetric unit) also displays the orientational disorder typical of thiophene rings: Ring 1, 55/45 (%) occupancy, ring 3, 70/30 occupancy, ring 4, 55/45 occupancy, ring 5, 85/15 occupancy, ring 7, 55/45 occupancy, and ring 8, 60/40 occupancy. The possibility exists that ring 6 (associated with S6) also possesses some minor disorder. The orientation of each disordered 2-thienyl ring in Fig. 6 is shown in the majority occupancy.

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Acknowledgements

Grateful acknowledgment is made of the EPSRC National Crystallography Service (Southampton, UK and Station 9.8, Daresbury, UK) and the Donors of the American Chemical Society Petroleum Research Fund for support of this research (Award 45312-B3 to DGH).

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Author notes

  1. Emily M. Harcourt

    Present address: Department of Chemistry, Le Moyne College, Syracuse, NY, 13214, USA

Authors and Affiliations

  1. Exilica Limited, The Technocentre, Puma Way, Coventry, CV1 2TT, UK

    Daniel E. Lynch

  2. Department of Chemistry, Mount Holyoke College, 50 College Street, South Hadley, MA, 01075, USA

    Emily M. Harcourt & Darren G. Hamilton

  3. Department of Chemistry, University of Akron, Akron, OH, 44325, USA

    James T. Engle & Christopher J. Ziegler

  4. Department of Chemistry, College of the Holy Cross, Worcester, MA, 01610, USA

    Joshua R. Farrell

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  1. Daniel E. Lynch
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Correspondence to Darren G. Hamilton.

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Lynch, D.E., Harcourt, E.M., Engle, J.T. et al. Crystal Structures of Cobalt Sandwich Complexes in the η5-Cyclopentadienyl/η4-Cyclobutadiene and η5-Cyclopentadienyl/η4-Cyclopentadienone Families. J Chem Crystallogr 50, 338–347 (2020). https://doi.org/10.1007/s10870-019-00806-4

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