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Pentacoordinated, square pyramidal cationic PCP Ni(II) pincer complexes: ELF and QTAIM topological analyses of nickel–triflate interactions

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Abstract

A previous report introduced a new series of cationic nickel(II) complexes ligated by PCP-type pincer ligands featuring a charge-bearing imidazoliophosphine binding moiety and described their catalytic reactivities in hydroamination of nitriles into amidines. Solid-state characterization of the cationic acetonitrile adducts [(R-PIMIOCOP+)Ni(NCMe)(triflate)]+ (R-PIMIOCOP+ = κP,κC,κP-{2-(R2PO),6-(R2PC4H5N2)C6H3}; R = i-Pr, [1]+; Ph, [2]+) carried out in this follow-up study showed a distorted square pyramidal geometry and a Ni–triflate distance that was shorter than the sum of the Ni and O van der Waals radii, features suggestive of an unusual pentacoordination at the Ni(II) center. In contrast, the related aquo adduct [(i-Pr-PIMIOCOP+)Ni(OH2)(triflate)]+, [3]+, displayed a more conventional square planar geometry. Detailed structural comparisons and theoretical analyses conducted on these and related compounds have allowed a thorough examination of the Ni–triflate interactions in this family of complexes. Thus, topological analysis of the electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM) showed that the Ni–triflate interaction is mostly ionic in nature, but has a weak covalence degree. The monosynaptic V(Ni) subvalence basin of nickel is indeed the ELF signature of the covalence degree of the ionic Ni–O bond, which can be quantified by the negative QTAIM energy density at the Ni–O bond critical point and by the absolute value of the ELF covariance 〈σ2(V(O), C(Ni))〉. The ionic character of the Ni–O bond is also reflected in an energy decomposition analysis, showing that this interaction is mostly electrostatic in nature. The computational analyses carried out on this family of complexes provide valuable insight into the character and relative strengths of various Ni–ligand interactions, and allow a number of useful conclusions, including the following: (1) significant Ni–anion interactions at the apical site are observed only with pincer-type ligands featuring at least one cationic imidazoliophosphine binding moiety; (2) these primarily electrostatic Ni–O interactions gain increasing covalence degree when different pincer backbone, co-ligand L, or counter-anions are introduced to enhance the electron deficiency of the Ni(II) center.

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Notes

  1. A series of pentacoordinated pincer complexes of the type (PCP)Ni(o-semiquinonato) has been shown to adopt square pyramidal geometry, but there is some ambiguity about whether these paramagnetic compounds should be considered trivalent (17-electron) or divalent (18-electron) species [11,12,13,14].

  2. The coordination plane in question is the least-squares plane defined by P1, C5, P2, and N3 in the acetonitrile adducts and by P1, C5, P2, O8 in the aquo adduct.

  3. The τ index is commonly used to categorize the geometry of a 5-coordinated species. Defined by the equation (β − α)/60 where β and α (in degrees) are the two largest valence angles of the coordination center (β > α), τ takes numerical values ranging from 0 (for an ideal square pyramidal geometry) to 1 (for an ideal trigonal bipyramidal geometry). The extent of distortion from the two ideal geometries can thus be estimated from the τ value calculated for a given 5-coordinated complex. For a discussion of τ index, see [15].

  4. The complete set of ELF data for complex [1]++ is presented in the Electronic Supporting Information of reference [9].

  5. This approach for estimating the formal oxidation number using ELF analysis was successfully applied to ambiguous cases, and the results were nicely correlated with the X-ray photoelectron spectroscopy results. See [19].

  6. The population of V(Ni) is insensitive to the accuracy level of the ELF analysis (grid size, approximation in the gradient field analysis), the location of the V(Ni) attractor, the volume, and the V(Ni) population depend on the type of double-zeta basis set (6-31G**, 6-31++G**, DGDZVP, …). See Table S1 in SI.

  7. For a classification of various ligands, see [27].

  8. Eint = ½ Vbcp and Eint (kcal/mol) = − 313.754 × Vbcp (au). See [29, 30].

  9. According to Refs. [20, 21], the electrostatic interaction between the metallic cation and the ligand is more polarized or covalent, when the number of monosynaptic basins describing the lone pair of the ligand increases. As a result, because of the differential polarizing field surrounding it, the cation splits its outer-shell density toward the ligands into localization domains called subvalence basins whose volume and population increase as the nature of the interaction becomes more covalent/polarized.

  10. Molekel 4.3 from CSCS: http://www.cscs.ch/molekel/.

  11. See references [50,51,52]

    Optionally, you may add the following list of authors and contributors:

    E.J. Baerends, T. Ziegler, J. Autschbach, D. Bashford, A. Bérces, F.M. Bickelhaupt, C. Bo, P.M. Boerrigter, L. Cavallo, D.P. Chong, L. Deng, R.M. Dickson, D.E. Ellis, M. van Faassen, L. Fan, T.H. Fischer, C. Fonseca Guerra, M. Franchini, A. Ghysels, A. Giammona, S.J.A. van Gisbergen, A.W. Götz, J.A. Groeneveld, O.V. Gritsenko, M. Grüning, S. Gusarov, F.E. Harris, P. van den Hoek, C.R. Jacob, H. Jacobsen, L. Jensen, J.W. Kaminski, G. van Kessel, F. Kootstra, A. Kovalenko, M.V. Krykunov, E. van Lenthe, D.A. McCormack, A. Michalak, M. Mitoraj, S.M. Morton, J. Neugebauer, V.P. Nicu, L. Noodleman, V.P. Osinga, S. Patchkovskii, M. Pavanello, P.H.T. Philipsen, D. Post, C.C. Pye, W. Ravenek, J.I. Rodríguez, P. Ros, P.R.T. Schipper, G. Schreckenbach, J.S. Seldenthuis, M. Seth, J.G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A. Wesolowski, E.M. van Wezenbeek, G. Wiesenekker, S.K. Wolff, T.K. Woo, A.L. Yakovlev.

  12. http://sites.google.com/site/allouchear/Home/gabedit.

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Acknowledgements

The theoretical studies were performed using HPC resources from CALMIP (Grant 2013-2018 [0851]]) and from GENCI-[CINES/IDRIS] (Grant 2013-2018 [085008]). The authors gratefully acknowledge the financial support provided by NSERC (Discovery grant to DZ) and FRQNT (Ph.D. fellowship to BV). The Direction des Relations Internationales of Université de Montréal and Université Toulouse 3-Paul Sabatier are gratefully acknowledged for the travel grants that made this collaborative project possible. The authors would like to thank Professor Bernard Silvi for fruitful discussions.

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Authors and Affiliations

  1. LCC-CNRS, Université de Toulouse, CNRS, Toulouse, France

    Christine Lepetit & Yves Canac

  2. Département de Chimie, Université de Montréal, Montréal, QC, H3C 3J7, Canada

    Boris Vabre & Davit Zargarian

  3. UPMC Université Paris 06, MONARIS, UMR 8233, Université Pierre et Marie Curie, Sorbonne Universités, 4 Place Jussieu, Case courrier 49, 75252, Paris Cedex 05, France

    Mohammad Esmaïl Alikhani

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  1. Christine Lepetit
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Correspondence to Christine Lepetit.

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Lepetit, C., Vabre, B., Canac, Y. et al. Pentacoordinated, square pyramidal cationic PCP Ni(II) pincer complexes: ELF and QTAIM topological analyses of nickel–triflate interactions. Theor Chem Acc 137, 141 (2018). https://doi.org/10.1007/s00214-018-2332-y

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