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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
First Online:
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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 
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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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Authors and Affiliations

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

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