Inorganica Chimica Acta 359 (2006) 44274430 www.elsevier.

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CH/p interactions of p-system of acetylacetonato chelate ring: Comparison of CH/p interactions of Ni(II)-acetylacetonato chelate and benzene rings
Milos K. Milcic, Vesna B. Medakovic, Snezana D. Zaric
Received 17 February 2006; received in revised form 10 May 2006; accepted 13 June 2006 Available online 22 June 2006

Department of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11001 Belgrade, Serbia and Montenegro

Abstract The calculations have been done for CH/p interaction with p-system of Ni(II)-acetylacetonato chelate ring. The results show that there is an attractive electrostatic interaction, while dispersion component is a major source of attractive interacting energies. The interaction was compared with CH/p interaction between two benzene rings. The comparison shows that two interactions are quite similar, enabling to estimate the energy of CH/p interaction with p-system of Ni(II)-acetylacetonato chelate ring to be about 10.5 kJ/mol. The results indicate that CH/p interactions of chelate ring in various molecular systems can be as important as CH/p interactions of phenyl ring. 2006 Elsevier B.V. All rights reserved.
Keywords: CH/p interaction; DFT; MP2; Chelate

1. Introduction There is intensive research of noncovalent interactions involving p-systems [142]. It was shown that these interactions are very important for many biological molecules [14]. Analyzing CH/p interactions in proteins shows that these interactions play an important role in the stability of proteins [1]. Transition metal complexes can be involved in XH/p interactions in two ways: as hydrogen atom donor or hydrogen atom acceptor [2339]. In the rst case, partially positive hydrogen atoms of coordinated ligands can interact with aromatic ring. This type of interaction is also called metal ligand aromatic cation-p (MLACp) interactions [2933]. In the second case, there is an interaction of CH bond with p-systems of planar chelate rings with delocalized bonds [3439]. The capability of
Corresponding author. Tel.: +381 11 3282 111; fax: +381 11 184 330. E-mail addresses: szaric@chem.bg.ac.yu, zaric@mail.chem.tamu.edu (S.D. Zaric). 0020-1693/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2006.06.022
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p-systems of chelate rings to be involved in noncovalent interactions in a similar way as aromatic rings could be connected with metalloaromaticity of chelate rings [34 42]. There are many unsolved questions about noncovalent interactions of chelate rings and about metalloaromaticity of chelate rings. Recent theoretical study of metallobenzene complexes, analogues of benzene where one CH unit has been replaced by an organometallic fragment, showed that they may be aromatic [43]. However, there is still very little known about the aromaticity of chelate rings with heteroatoms. One of these chelate rings that show some of the aromatic properties is acetylacetonato chelate ring [44]. In order to elucidate noncovalent interactions of potentially aromatic chelate rings, and similarity with interactions of organic aromatic rings, here we present theoretical results about CH/p interaction of p-system of Ni(II)-acetylacetonato chelate ring and comparison with CH/p interaction of p-systems of benzene. Electrostatic and dispersion component of CH/p interactions of Ni(II)-acetylacetonato chelate ring

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have been estimated for the rst time. Moreover, a comparison with very accurate calculations on CH/p interactions in benzene dimer enabled to estimate interacting energies. 2. Computational methods All ab initio and DFT energy calculations were carried out using the GAUSSIAN 98 program [45]. The model system for calculations of CH/p interactions of benzene with p-system of acetylacetonato chelate ring (Fig. 1a) was made from XIBRUV crystal structure [46], which was taken from CSD [47]. Since crystal structures sometimes display unrelaxed intramolecular geometries yielding distorted wave functions and wrong energies, we rst optimized the crystal coordinates of the individual CH/p partners. In the case of benzenebenzene interactions, we optimized benzene molecule in D6h geometry. All optimizations have been done using DFT, specically Becke three-parameter exchange functional (B3) [48] and the LeeYangParr correlation functional (LYP) [49], level of theory. The LANL2DZ basis set was chosen for nickel atom and the 6-31G** basis set was chosen for carbon, oxygen, nitrogen and hydrogen atoms. These optimized structures for both model systems were then reassembled into geometries optimal for CH/p interactions (Fig. 1). MP2 single point calculations, with the same basis set, were done using B3LYP optimized structures. The interaction energy DE is dened as the dierence between the energy of the complexes AB and the energy of the isolated partners, i.e. DE = E(A B) E(A) E(B). The standard counterpoise method was applied to correct MP2 calculated interaction energies for the basis set superposition error (BSSE) [50].

3. Results and discussion The calculations have been done for CH/p interaction of benzene molecule with acetylacetonato chelate ring of Ni(II) complex (Fig. 1a). Ni(II)-acetylacetonato chelate ring was a part of the model system made from XIBRUV crystal structure. Single point calculations were done for distances from 2.1 to 3.5 A between center of the ring (X) and hydrogen atom from benzene molecule (Fig. 2). For comparison, calculations with the same methods have also been done for CH/p interaction in T-shape benzene dimer (Figs. 1b and 2). For the calculations, B3LYP and MP2 methods were used. Because of large basis set superposition error (BSSE) in case of MP2 method, only MP2 data corrected for BSSE are presented. B3LYP method was used as the most popular DFT method, MP2 was used since previous calculations on benzene dimer showed that MP2 method is a reasonably good method for calculating the geometry of T-shape benzene with CH/p interactions [1922]. Also, comparison of B3LYP and MP2 methods enables to make a conclusions about the nature of the CH/p interaction of chelate ring. Namely, B3LYP method can well recognize electrostatic component but not dispersion component, while MP2 method can well recognize dispersion component. The interacting energies with B3LYP method for benzenechelate and benzenebenzene are quite similar, at the minima the energies are 2.86 and 2.69 kJ/mol, respectively (Table 1, Fig. 2). Negative energies obtained for B3LYP method show that there is an attractive electrostatic interaction for both Ni(II)-acetylacetonato chelate (Fig. 1a) and benzene ring (Fig. 1b). Results for benzene are in agreement with previous results that show that T-shaped benzene dimer is stabilized by the attractive elec-

12 10 8 6

B3LYP (Bz-Bz) B3LYP (Bz-Ch) MP2 (Bz-Bz) MP2 (Bz-Ch)

E i (kJ/mol)

4 2 0
2.1 2.3 2. 5 2.7 2.9 3.1 3.3

3.5

3.7

-2 -4 -6 -8

Fig. 1. Model systems for calculations of CH/p interaction (a) of benzene ring with Ni(II)-acetylacetonato chelate ring of complex made from the crystal structure XIBRUV [46] and (b) between two benzene molecules in T-shape position.

Distance ()

Fig. 2. Diagram showing the results of single point energy calculations of CH/p interactions for dierent H X distances for benzenebenzene (Bz Bz) and benzenechelate (BzCh) (Fig. 1).

 M.K. Milcic et al. / Inorganica Chimica Acta 359 (2006) 44274430 Table 1 Interaction energies at the minima for benzenechelate and benzene benzene using MP2 and B3LYP methods Benzenechelate Ei (kJ/mol) B3LYP MP2 2.86 6.78 Distance (A) 2.8 2.6 Benzenebenzene Ei (kJ/mol) 2.69 6.60 Distance (A) 2.9 2.7

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plexes. These interactions can inuence the interactions of metal complexes in solution and other environments. Acknowledgement The authors would like to thank Prof. M. B. Hall for the support. This work was supported by the Serbian Ministry of Science (Grant 142037). References
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trostatic interaction [22]. Somewhat larger B3LYP energy for Ni(II)-acetylacetonato chelate ring shows that the electrostatic components are stronger for the interactions of Ni(II)-acetylacetonato chelate ring. The interacting energies with MP2 method for benzene chelate and benzenebenzene are again very similar; at the minima the energies are 6.78 and 6.60 kJ/mol, respectively (Table 1, Fig. 2). The origin of the larger energy for chelate ring is stronger electrostatic component, as was shown in B3LYP calculations. A comparison of the energies obtained with MP2 and B3LYP methods shows that B3LYP method underestimates interactions, as was anticipated since DFT methods are not able to describe dispersion component of the interactions. In both cases, calculated B3LYP interacting energy is by 3.9 kJ/mol smaller than MP2 energy (Table 1). It indicates that dispersion component is a major component in interacting energy and that CH/p interaction of Ni(II)-acetylacetonato chelate ring has almost the same contribution of dispersion component as CH/p interaction of benzene. Again, the results for benzene are in agreement with previous results that show that for T-shaped benzene the major source of attraction is dispersion interaction [22]. For both methods the minima are deeper for benzene chelate interaction, and whole curves are at somewhat lower energy (Fig. 2). At the same time, the minima of the curves are at shorter distances for benzenechelate than for benzene dimer interaction. For MP2 method the min ima are at 2.6 and 2.7 A, while for B3LYP method they are at 2.8 and 2.9 A, respectively (Table 1). Both energies and distances are indicating that CH/p interaction of Ni(II)-acetylacetonato chelate ring in the model system of XIBRUV crystal structure (Fig. 1a) is somewhat stronger than CH/p interaction of benzene ring (Fig. 1b). The results, for the rst time, show that CH/p interactions of benzene ring and Ni(II)-acetylacetonato chelate ring are quite similar (Fig. 2). Previous, very accurate calculations on T-shaped benzene dimer show that the interacting energy is about 10.0 kJ/mol [1922]. Based on that, we can estimate that CH/p interaction with Ni(II)acetylacetonato chelate ring in our model system (Fig. 1a) is about 10.5 kJ/mol. It was shown that CH/p interactions of phenyl rings are very important in dierent molecular systems, especially in biomolecules [14]. Because of similar interacting energies of p-system of acetylacetonato chelate and phenyl rings, CH/p interactions of chelate rings can have similar importance in molecular systems with transition metal com-

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