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Structural Chemistry

, Volume 30, Issue 1, pp 107–114 | Cite as

Are there analogues of the indenyl effect in larger ring systems: a DFT study of hydride attack on [Mn(CO)3(naphthalene)]+ and [Cr(CO)3(benzotropylium)]+

  • Abdulhakim A. AhmedEmail author
Original Research
  • 53 Downloads

Abstract

Two pairs of complexes, [Mn(CO)3(benzene)]+/[Mn(CO)3(naphthalene)]+ and [Cr(CO)3(tropylium)]+/[Cr(CO)3(benzotropylium)]+, have been used as a platform to establish the extent to which the well-known ‘indenyl effect’ translates into other bicyclic ligand systems. Density functional theory (DFT) suggests that the ‘naphthalene effect’ is minimal, the pathway for hydride reduction of [Mn(CO)3(naphthalene)]+ resembling closely that for the benzene analogue. In the benzotropylium system, in contrast, stabilisation of an η5 coordination mode through aromatisation of the six-membered ring plays a similar role to stabilisation of η3 in the indenyl effect. The greater influence of aromatisation in the five- and seven-membered ring systems stems from the presence of formal charge on the ligands in these cases: localisation of this charge on a subset of the available carbon atoms enhances the electrostatic component of the metal-ligand bond. This is particularly dramatic in the benzotropylium case, where the η7–η5 slippage corresponds to a formal 2-electron reduction of the ligand from [C7H7]+ to [C7H7].

Keywords

Indenyl effect DFT Naphthalene effect Tropylium and hydride attack 

Notes

Acknowledgments

The author is indebted to Professor J. E. McGrady and his group at theoretical chemistry laboratory, Oxford University, for their assistance throughout the work.

Supplementary material

11224_2018_1179_MOESM1_ESM.docx (31 kb)
ESM 1 (DOCX 30 kb)

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Departments of Chemistry, Faculty of ScienceUniversity of BenghaziBenghaziLibya

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