Vol 44, No 2 (2018)

The reaction of Ag(CH₃SO₃) with PPh₃ gave the compound [Ag(CH₃SO₃)(PPh₃)₂] (I) and the reaction of Ag(CH₃SO₃) with PPh₃ and 1,2-bis(4-pyridyl)ethane (Dpe) affords the mixed complex [Ag(CH₃SO₃)(PPh₃)(Dpe)] (II). The crystal structures of I and II were determined by X-ray diffraction (CIF file CCDC no. 1563357 (for I)). In I, the centrosymmetric binuclear complex [Ag(CH₃SO₃)-(PPh₃)₂]₂ is formed. The Ag atom has a distorted tetrahedral coordination composed of two bidentate bridging O atoms of the sulfonate anion and two P atoms of two PPh₃ ligands. The structure of II is based on the centrosymmetric binuclear molecule with two bridging Dpe ligands between two [Ag(CH₃SO₃)(PPh₃)] complexes. The O atoms of the methanesulfonate ion are statistically disordered, which induces a considerable distortion of the silver polyhedron with C.N. 5. Both compounds tend to emit in the blue and green regions of the PL spectra.

Complexes [CuL¹Cl₂] (I), [CuL²Cl₂] · EtOH (II), and Cu₂L³Cl₄ (III) containing esters of the N-derivatives of optically active amino acids based on (+)-3-carene (L¹, L²) and (‒)-α-pinene (L³) are synthesized. The crystal and molecular structures of compounds I and II are determined by X-ray diffraction analyses (CIF files CCDC nos. 1560071 (I), 1560072 (II)). The crystal structure of compound I consists of mononuclear complex molecules. In the structure of compound II, the unit cell contains two crystallographically independent molecules of mononuclear complex [CuL²Cl₂] and two EtOH molecules. Ligands L¹ and L² perform the tridentate-chelating function by the N atoms of the NH and NOH groups and by the O atom of the C=O group. In compounds I and II, the coordination polyhedra Cl₂N₂O of the Cu atoms are trigonal bipyramid. According to the data of IR and electronic spectroscopy, binuclear complex III has similar coordination polyhedra. The experimental values of μ_eff for compounds I, II, and III at 300 K are 1.93, 1.88, and 2.71 μB. For complex III, the μ_eff(T) dependence in a range of 2–300 K indicates a weak ferromagnetic exchange interaction.

A new coordination polymer of Cu(II) based on 1-phenyl-3-methyl-4-formyl-5-hydroxypyrazole 4,6-dimethylpyrimidylhydrazone is synthesized. The polymer is studied by X-ray diffraction analysis (CIF file CCDC no. 1565772). It is shown that the polymer is formed due to the coordination of the nitrogen atom of the pyrazolone fragment to the copper(II) ion of the adjacent monomeric fragment.

The reactions of [(L^iPrNi)₂(μ-η²:η²-S₄)] (I) and [(L^iPrNi)₂(μ-η²:η²-Se₂)] (II) (L^iPr = CH[C(Me)N(2,6-ⁱPr₂C₆H₃)]₂) with decamethylsamarocene [Sm(Cp*)₂(Тhf)₂] (Cp* = η⁵-C₅Me₅) are studied. It is assumed that the reactions afford hetero-d/f-metal complexes. However, these complexes are not observed but the transfer of chalcogens from Ni to Sm and the formation of [(Sm(Cp*)₂(Тhf))₂(μ-S)] (III) and [(Sm(Cp*)₂(Тhf))₂(μ-Se)] (IV) occur. The second reaction products are [(L^iPrNi)₂(μ-η²:η²-S₂)] (V) in the case of sulfur and [(L^iPrNi^I)₂(μ-η⁶:η⁶-C₇H₈)₂] (VI) in the case of selenium. All reaction products have been described previously, but compounds III and V are isolated as new crystalline phase, the structures of which are determined by X-ray diffraction analysis (CIF files CCDC nos. 1559045 (V) and 1559046 (III)).

The oxidative addition of bis-o-benzoquinone Q–(CH=N–N=CH)–Q (L), in which two 3,5-ditert-butyl-o-benzoquinones are linked to each other in positions 6 via the CH=N–N=CH group, to triphenylstibine gave a new binuclear triphenylantimony(V) bis-catecholate complex, Ph₃Sb(Cat–(CH=N–N=CH)–Cat)SbPh₃ (I). Recrystallization of I from a methanol–trichloromethane mixture resulted in an additional coordination of a methanol molecule to each antimony atom to give the binuclear complex, (CH₃OH)Ph₃Sb(Cat–(CH=N–N=CH)–Cat)SbPh₃(CH₃OH) (I · 2CH₃OH), the crystals of which (I · 2CH₃OH) · 2CH₃OH · CHCl₃ (II) contain additionally two methanol solvate molecules, which fix the geometry of the nitrogen-containing bridging group, and a trichloromethane molecule. The molecular structure of compound II in the crystalline state was determined by X-ray diffraction (CIF file CCDC no. 1560840).