THEORETICAL INORGANIC CHEMISTRY

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1 I , Russian Journal of Inorganic hemistry, 009, Vol. 54, o. 1, pp Pleiades Publishing, Inc., 009. riginal Russian Text D.V. hachkov,.v. Mikhailov, 009, published in Zhurnal eorganicheskoi Khimii, 009, Vol. 54, o. 1, pp TERETIAL IRGAI EMITRY DFT B3LYP alculation of the patial tructure of o(ii), i(ii), and u(ii) Template omplexes Formed in Ternary ystems Metal(II) Ion Dithiooxamide Formaldehyde D. V. hachkov and. V. Mikhailov Kazan tate Technological University. ul. Karla Marksa 68, Kazan, Tatarstan, Russia Received July 17, 008 Abstract The hybrid density functional theory B3LYP method with the 6-31G(d) basis set and the Gaussian 98 program has been used for calculating the geometric parameters of the Mn(II), o(ii), i(ii), and u(ii) es with -donor macrocyclic ligands forming in the course of template processes in the M(II) dithiooxamide formaldehyde systems. The bond lengths and bond angles in the es with the M metal chelate core are reported. For all M(II) ions, the extra six-membered chelate ring that form as a result of template assembly is rotated through a rather large angle with respect to two five-membered rings and the ring itself is not planar. DI: / The template synthesis in ternary systems M(II) ion dithiooxamide ( (=) (=) ) formaldehyde (M = o, i, u) that occurs in metal(ii) hexacyanoferrate(ii) gelatin-immobilized matrices (MF GIM) and specific features of the coordination of the nascent ligand (chelant) to the corresponding metal ion have been studied [1 3]. owever, the spatial structure of es formed in these systems has not been studied so far since the available methods of their isolation from the reaction system fail to provide crystals suitable for X-ray crystallographic study. Therefore, it is pertinent to use a modern ab initio quantumchemical method for calculating the metal es formed in these systems to obtain independent objective data on their geometric parameters. MPUTATIAL METD Quantum-chemical calculations were performed with the use of the hybrid density functional theory B3LYP method with the 6-31G(d) basis set, based on a combination of the artree Fock method and the density functional theory [4]. The calculations were performed with the Gaussian 98 program [5]. Each core atomic orbital was described by six Gaussian-type functions (GT), each valence s A was described by three GTs, and each valence p A was described by one GT augmented with a polarization d GT. In all cases, the correspondence of the found stationary points to energy minima was checked by calculation of the essian (all positive eigenvalues). Preliminary tests of this method performed on various 3d-metal chelates showed that it is able to reliably calculate basic geometric parameters of their structures (artesian coordinates of all atoms, bond lengths, bond angles, and dihedral angles). All quantum-chemical calculations were performed at the upercomputer enter, Kazan cientific enter, RA. REULT AD DIUI According to [1 3], in the es formed in the course of template synthesis in the o(ii) dithiooxamide formaldehyde, i(ii) dithiooxamide formaldehyde, and u(ii) dithiooxamide formaldehyde systems, the template ligand is coordinated to the metal(ii) ion in the,,,-coordination mode. The template processes that occur in these ternary systems are described by overall schemes (1), (), and (3), respectively: o [Fe() 6 ] o i + [Fe() 6 ] i [Fe() 6 ] [Fe() 6 ] (1) () 195

2 DFT B3LYP ALULATI 1953 u [Fe() 6 ] u (3) In all cases, these processes lead to the formation of macrocyclic o(ii), i(ii), and u(ii) es in which,8-dithio-3,7-diaza-5-oxanonanedithioamide-1,9 acts as a chelant. The,,,-coordination of this ligand to the above metal ions is generally consistent with the Pearson AB concept [6, 7]. The calculated structures of es with similar coordination are shown in the figure, and the bond lengths and bond angles are listed in Tables 1 3. As follows from these data, for the cobalt(ii) and copper(ii) es with the above chelant, the coplanar orientation of its donor centers with respect to the corresponding central ion is preferable, the spin multiplicity M of the ground state being 4 and, respectively. For the i(ii), the tetrahedral coordination with the triplet ground state is preferable. The difference in the energies of structures with a spin multiplicity other than the multiplicity of the ground state (doublet for o(ii), singlet for i(ii), and quartet for u(ii)) is 15.6, 30.4, and kj/mol, respectively. The average M and M bond lengths in the es with a planar chelate core are, respectively, 0.9 and 7.4 pm for o(ii) and 07.4 and 6.7 pm for u((ii). In the i(ii) with the tetrahedral chelate core, these bonds are noticeably shorter than in the o(ii) and u(ii) es. These bond lengths are rather different (the i bond lengths are 09.1 and 09.6 pm, and the i bond lengths are 4.4 and 4.8 pm). It is worth noting that the extra six-membered ring formed due to template assembly is not coplanar with the metal chelate core M ; in all cases, the six-membered ring is inclined to the M core (by 67.4 for o, ~46 for i, and 68.4 for u). The six-membered ring itself is also nonplanar: the oxygen atom in it is out of the plane by an angle of 74.8 (o), ~79 (i), and 73.4 (u). It should be noted that the nitrogen and oxygen atoms of this extra ring in the o(ii) and u(ii) es are in the same plane, whereas in the i(ii), there is a deviation, even if small one, of one of these atoms from the plane through the other three atoms (because of this the ~ sign is placed in front of the values of the above angles for this ). As for the metal chelate core M, it is nearly planar only in the copper(ii) ; In the cobalt(ii), only the donor atoms are coplanar; in the nickel(ii), only three of the four donor atoms are in the same plane. It is worth noting that the result of the calculation of the structure and multiplicity of the nickel is + [Fe() 6 ] Table 1. alculated geometric parameters of the o(ii) length d, pm 1 d(1,) 17.5 A(,1,14) 110. A(4,13,5) 85.7 d(1,14) 10.5 A(1,,3) A(4,13,1) d(,3) A(1,,4) 18.0 A(5,13,7) 81.0 d(,4) A(3,,4) A(7,13,1) 85.7 d(3,5) A(,3,5) A(19,18,0) d(3,6) A(,3,6) 15.0 A(5,19,18) d(4,13) 7.5 A(5,3,6) 11.1 A(5,19,1) d(5,13) 0.9 A(,4,13) 99.8 A(5,19,) d(5,15) 10.3 A(3,5,13) A(18,19,1) d(5,19) A(3,5,15) A(18,19,) 11.9 d(7,8) A(3,5,19) A(1,19,) d(7,13) 0.9 A(13,5,15) A(7,0,18) d(7,16) 10.3 A(13,5,19) A(7,0,3) d(7,0) A(15,5,19) A(7,0,4) d(8,9) A(8,7,13) A(18,0,3) 11.9 d(8,10) A(8,7,16) A(18,0,4) d(9,11) 17.5 A(8,7,0) A(3,0,4) d(9,1) A(13,7,16) d(11,17) 10.5 A(13,7,0) d(1,13) 7.5 A(16,7,0) d(18,19) A(7,8,9) d(18,0) A(7,8,10) 11.1 d(19,1) A(9,8,10) 15.1 d(19,) A(8,9,11) d(0,3) A(8,9,1) d(0,4) A(11,9,1) 18.0 A(9,11,17) 110. A(9,1,13) o RUIA JURAL F IRGAI EMITRY Vol. 54 o

3 1954 RUIA JURAL F IRGAI EMITRY Vol. 54 o AKV, MIKAILV i i o u u o (A) (B) () patial structure of the (A) o(ii), (B) i(ii), and () u(ii) template es with,8-dithio-3,7-diaza-5-oxanonanedithioamide-1,9: front view and side view.

4 DFT B3LYP ALULATI 1955 Table. alculated geometric parameters of the i(ii) i Table 3. alculated geometric parameters of the u(ii) u length d, pm length d, pm d(1,) 17.3 A(,1,14) A(9,1,13) 96.5 d(1,14) 10.5 A(1,,3) A(4,13,5) 86.1 d(,3) 151. A(1,,4) 17.8 A(4,13,1) 17.9 d(,4) A(3,,4) A(5,13,7) 89.3 d(3,5) 14.5 A(,3,5) A(7,13,1) 88.4 d(3,6) A(,3,6) 15.4 A(19,18,0) d(4,13) 4.4 A(5,3,6) 13.5 A(5,19,18) 108. d(5,13) 09.6 A(,4,13) 95.4 A(5,19,1) d(5,15) 10.4 A(3,5,13) 10.0 A(5,19,) d(5,19) A(3,5,15) A(18,19,1) d(7,8) A(3,5,19) A(18,19,) 11.6 d(7,13) 09.1 A(13,5,15) A(1,19,) d(7,16) 10.3 A(13,5,19) A(7,0,18) d(7,0) A(15,5,19) 109. A(7,0,3) d(8,9) A(8,7,13) A(7,0,4) d(8,10) 16.8 A(8,7,16) A(18,0,3) 11.3 d(9,11) 17.4 A(8,7,0) A(18,0,4) d(9,1) A(13,7,16) 113. A(3,0,4) d(11,17) 10.5 A(13,7,0) d(1,13) 4.8 A(16,7,0) d(18,19) A(7,8,9) 11.8 d(18,0) A(7,8,10) 11.6 d(19,1) A(9,8,10) 15.5 d(19,) A(8,9,11) d(0,3) A(8,9,1) 113. d(0,4) A(11,9,1) 18.5 A(9,11,17) d(1,) 17.7 A(,1,14) A(4,13,5) 87.5 d(1,14) 10.5 A(1,,3) A(4,13,1) 95.9 d(,3) A(1,,4) 18.6 A(5,13,7) 85.9 d(,4) A(3,,4) A(7,13,1) 87.5 d(3,5) A(,3,5) 113. A(19,18,0) d(3,6) 16.8 A(,3,6) 15.8 A(5,19,18) d(4,13) 6.7 A(5,3,6) 10.9 A(5,19,1) d(5,13) 07.4 A(,4,13) 98. A(5,19,) d(5,15) 10.3 A(3,5,13) A(18,19,1) d(5,19) A(3,5,15) A(18,19,) 11.9 d(7,8) A(3,5,19) A(1,19,) 110. d(7,13) 07.4 A(13,5,15) A(7,0,18) d(7,16) 10.3 A(13,5,19) A(7,0,3) d(7,0) A(15,5,19) A(7,0,4) d(8,9) A(8,7,13) A(18,0,3) 11.9 d(8,10) 16.8 A(8,7,16) A(18,0,4) d(9,11) 17.7 A(8,7,0) A(3,0,4) 110. d(9,1) A(13,7,16) d(11,17) 10.5 A(13,7,0) d(1,13) 6.7 A(16,7,0) d(18,19) A(7,8,9) 113. d(18,0) A(7,8,10) 10.9 d(19,1) A(9,8,10) 15.8 d(19,) A(8,9,11) d(0,3) A(8,9,1) d(0,4) A(11,9,1) 18.6 A(9,11,17) A(9,1,13) 98. RUIA JURAL F IRGAI EMITRY Vol. 54 o

5 1956 AKV, MIKAILV inconsistent with the data in [8]. According to the latter, this is diamagnetic and has brown color, which is typical of planar rather than tetrahedral i(ii) es [9]. This inconsistency can be due to the fact that the results of these calculations are, first of all, valid for processes in the gas phase rather than in MF GIM, in which the i(ii) was synthesized. In addition, it is well known that es of some dmetals with definite coordination numbers, including i(ii) with = 4, can change their spatial structure when transferred from one phase to another [9]. ere, further studies are evidently required. AKWLEDGMET This work was supported by the Russian Foundation for Basic Research (project no ). REFEREE 1.. V. Mikhailov, A. I. Khamitova, L.. higapova, and T.. Busygina, Trans. Met. hem. 4 (5), 503 (1999)... V. Mikhailov and A. I. Khamitova, Trans. Met. hem. 5 (1), 6 (000). 3.. V. Mikhailov, A. I. Khamitova, and V. I. Morozov, eterocycl. ommun. 6 (), 137 (000). 4. A. D. Becke, J. hem. Phys. 98 (7), 137 (1993). 5. M. J. Frisch, G. W. Trucks,. B. chlegel, et al., Gaussian 98 (Gaussian, Inc., Pittsburgh, 1998). 6. Yu.. Kukushkin, oordination hemistry (Vysshaya hkola, Moscow, 1985) [in Russian]. 7. R. J. Pearson, J. Am. hem. oc. 85 (), 3533 (1963). 8.. V. Mikhailov, Int. J. Inorg. Mater. 3 (7), 1053 (001). 9. F. A. otton and G. B. Wilkinson, Advanced Inorganic hemistry, 5th ed. (Wiley, ew York, 1990). RUIA JURAL F IRGAI EMITRY Vol. 54 o