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Theoretical description of bonding in cis-W(CO)4(piperidine)2 and its dimer

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Abstract

The gradient-corrected DFT calculations were applied to characterize the bonding in the cis-W(CO)4(piperidine)2 complex and its dimer. The Nalewajski–Mrozek bond order analysis, the Ziegler–Rauk bond-energy partitioning and Natural Orbitals for Chemical Valence (NOCV’s) were applied in a description of the electronic structure of cis-W(CO)4(piperidine)2. The results indicate that the metal-carbon bond trans to piperidine is stronger than that in the cis position, as a result of an increase in both, the ligand→ metal donation and metal → ligand π-back-bonding; this implies a weakening of the carbon–oxygen bond. In the dimeric complex, modeling the interactions in the solid state, the C–O bond is further weakened resulting in the lowering the CO stretching frequencies, observed experimentally by Braunstein et al. (Angew. Chem. Int. Ed. (2004), 43:5922–5925).

Interaction of cis-W(CO)4(piperidine)2 units in solid state together with NOCV's based bonding analysis.

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Authors and Affiliations

  1. Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060, Cracow, Poland

    Mariusz P. Mitoraj & Artur Michalak

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  1. Mariusz P. Mitoraj
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  2. Artur Michalak
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Correspondence to Artur Michalak.

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Mitoraj, M.P., Michalak, A. Theoretical description of bonding in cis-W(CO)4(piperidine)2 and its dimer. J Mol Model 16, 337–342 (2010). https://doi.org/10.1007/s00894-009-0545-7

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  • DOI: https://doi.org/10.1007/s00894-009-0545-7

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