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Of all publications in the section: 6
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Article
Mainichev D. A., Anyushin A., Moroz N. et al. Inorganic Chemistry. 2012. Vol. 51. No. 18. P. 9995-10003.

The coordination of Cd2+ with P(CH2OH)3 (THP) in methanol was followed by 31P and 113Cd NMR techniques. A cadmium-to-phosphine coordination ratio of 1:3 has been established, and effective kinetic parameters have been calculated. Air oxidation of THP in the presence of CdCl2 at room temperature produces coordination polymer 3∞[Cd3Cl6(OP(CH2OH)3)2]. The same oxidation reaction at 70 °C gives another coordination polymer, ∞[CdCl2(OP(CH2OH)3)]. These complexes are the first structurally characterized complexes featuring OP(CH2OH)3 as a ligand that acts as a linker between Cd atoms. The addition of NaBPh4 to the reaction mixture gives coordination polymer ∞[Na2CdCl2(O2P(CH2OH)2)2(H2O)3] with (HOCH2)2PO2− as the ligand.

Added: Nov 13, 2014
Article
Ananyev I., Бикбаева З., Иванов Д. et al. Inorganic Chemistry. 2017. Vol. 56. No. 21. P. 13562-13578.

The nitrosoguanidinate complex [Ni{NH=C(NMe2)-NN(O)}(2).] (1) was cocrystallized with I-2 and sym-trifluorotriiodo-benzene (FIB) to give associates 1.2I(2) and 1.2FIB. Structures of these solid species were studied by XRD followed by topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) at the M06/DZP-DKH level of theory and Hirshfeld surface analysis. Our results along with inspection of XRD (CCDC) data, accompanied by the theoretical calculations, allowed the identification of three types of contacts. The Ni center dot center dot center dot I semicoordination of the electrophilic nickel(II) center with electron belt of 12 was observed in 1.2I(2), the metal -involving halogen bonding between the nucleophilic nickel(II)-d(z)(2) center and sigma-hole of iodine center was recognized and confirmed theoretically in the structure of [FeNi(CN)(4)(IPz)(H(2)0)](n) (IPz = 4-N-coordinated 2-I-pyrazine), whereas the arrangement of FIB in 1.2FIB provides a boundary case between the semicoordination and the halogen Ni center dot center dot center dot I bondings. In 1.2I(2) and 1.2FIB, noncovalent interactions were studied by variable temperature XRD detecting the expansion of noncovalent contacts with preservation of covalent bond lengths upon the temperature increase from 100 to 300 K. The nature and energies of all identified types of the Ni center dot center dot center dot I noncovalent interactions in the obtained (1.2I(2) and 1.2FIB) and in the previously reported ([FeNi(CN)(4)(IPz)(H2O)](n) [NiL2](I-3)(2)center dot 2I(2) (L = o-phenylene-bis(dimethylphosphine),[NiL]I-2 (L = 1,4,8,11-tetra-azacydotetradecane), Ni(en)(2)](n)[AgI2](2n) (en = ethylenediamine), and [NiL] (ClO4) (L = 4-iodo-2-(2-(2-(2-pyridyl)ethylsulfanypethylimino)methyl)-phenolate)) structures were studied theoretically. The estimated strengths of these noncovalent contacts vary from 1.6 to 4.1 kcal/mol and, as expected, become weaker on heating. This work is the first emphasizing electrophilic nucleophilic dualism of any metal center toward noncovalent interactions.

Added: Oct 4, 2019
Article
Larionov V. A., Yashkina L. V., Медведев М. Г. et al. Inorganic Chemistry. 2019. Vol. 58. No. 16. P. 11051-11065.

Chiral copper(II) and cobalt(III) complexes (1–5 and 6, respectively) derived from Schiff bases of (S)-2-(aminomethyl)pyrrolidine and salicylaldehyde derivatives were employed in a mechanistic study of the Henry reaction-type condensation of nitromethane and o-nitrobenzaldehyde in CH2Cl2 (CD2Cl2), containing different amounts of water. The reaction kinetics was monitored by 1H and 13C NMR. The addition of water had a different influence on the activity of the two types of complexes, ranging from a crucial positive effect in the case of the copper(II) complex 2 to insignificant in the case of the stereochemically inert cobalt(III) complex 6. No experimental support was found by 1H NMR studies for the classical Lewis acid complexation of the carbonyl group of the aldehyde by the central copper(II) ion, and, moreover, density functional theory (DFT) calculations support the absence of such coordination. On the other hand, a very significant complexation was found for water, and it was supported by DFT calculations. In fact, we suggest that it is the Brønsted acidity of the water molecule coordinated to the metal ion that triggers the aldehyde activation. The rate-limiting step of the reaction was the removal of an α-proton from the nitromethane molecule, as supported by the observed kinetic isotope effect equaling 6.3 in the case of the copper complex 2. It was found by high-resolution mass spectrometry with electrospray ionization that the copper(II) complex 2 existed in CH2Cl2 in a dimeric form. The reaction had a second-order dependence on the catalyst concentration, which implicated two dimeric forms of the copper(II) complex 2 in the rate-limiting step. Furthermore, DFT calculations help to generate a plausible structure of the stereodetermining transition step of the condensation.

Added: Oct 10, 2019
Article
Kirsanova M. A., Akmaev A. S., Aksyonov D. A. et al. Inorganic Chemistry. 2020. Vol. 59. No. 22. P. 16225-16237.

A new monoclinic α-polymorph of the Na2FePO4F fluoride-phosphate has been directly synthesized via a hydrothermal method for application in metal-ion batteries. The crystal structure of the as-prepared α-Na2FePO4F studied with powder X-ray and neutron diffraction (P21/ca = 13.6753(10) Å, b = 5.2503(2) Å, c = 13.7202(8) Å, β = 120.230(4)°) demonstrates strong antisite disorder between the Na and Fe atoms. As revealed with DFT-based calculations, α-Na2FePO4F has low migration barriers for Na+ along the main pathway parallel to the b axis, and an additional diffusion bypass allowing the Na+ cations to go around the Na/Fe antisite defects. These results corroborate with the extremely high experimental Na-ion diffusion coefficient of (1–5)·10–11 cm2·s–1, which is 2 orders of magnitude higher than that for the orthorhombic β-polymorph ((5–10)·10–13 cm2·s–1). Being tested as a cathode material in Na- and Li-ion battery cells, monoclinic α-Na2FePO4F exhibits a reversible specific capacity of 90 and 80 mAh g–1, respectively.

Added: Feb 10, 2021
Article
Mainichev D. A., Sokolov M., Adonin S. et al. Inorganic Chemistry. 2013. Vol. 52. No. 16. P. 9675-9682.

New Ru-substituted Keggin-type polyoxometalate complex containing nitroso ligand, [PW11O39Ru(NO)]4-, has been prepared. It is converted by hydrazin or hydroxylamine into aqua complex [PW11O39RuIII(H2O)]4- in quantitative yield. Intermediate complex of dinitrogen has been detected. Sn2+ converts [PW11O39Ru(NO)]4- into [PW11O39Ru(NH3)]4-.

Added: Nov 13, 2014
Article
Roitershtein D., Puntus L. N., Nifant'ev I. E. et al. Inorganic Chemistry. 2018. Vol. 57. No. 16. P. 10199-10213.

A new approach to design “antenna-ligands” to enhance the photoluminescence of lanthanide coordination compounds based on π-type ligand - polyphenylsubstituted cyclopentadienyl has been developed. The complexes of di-, tri- and tetraphenyl cyclopentadienyl ligands with Tb and Gd has been synthesized and all the possible structural types from mononuclear to di- and tetranuclear as well as coordination polymer were obtained. All types of the complexes have been studied by single-crystal X-ray diffraction and optical spectroscopy. All complexes are luminescent at ambient temperature and two of them have relatively high quantum yields (50 and 60%). Analysis of energy transfer process has been performed and supported by quantum chemical calculations. The role of a low-lying intraligand charge transfer state formed by extra coordination with K+ in the Tb+3 ion luminescence sensitization is discussed. New aspects for design of lanthanide complexes containing π-type ligands with desired luminescence properties have been proposed.

Added: Oct 18, 2018