Aleksey A. Sidorov

IMIDO/NITRENE LIGANDS IN THE COMPLEXES OF PLATINUM METALS

A synthetic search for palladium and platinum complexes with nitrene ligands via reaction of tetranuclear cluster Pd 4 ( μ 2 -CO) 4 ( μ 2 -OAc) 4 with nitrosobenzene and reactions of mononuclear complexes [MX 4 ] 2− (M=Pt, Pd; X=Cl, NO 2 ) with o -phenylenediamine and its N -phenyl derivative have been carried out. The complexes obtained, [Pd(OAc) o -(PhN)(NO)C 6 H 4 ] 2 , Pd[ o -(NPh)(N)C 6 H 4 ] 2 , Pt[ o -(NPh)(N)C 6 H 4 ] 2 , Pt 2 [ o -(NPh)(N)C 6 H 4 ] 4 [O 3 SCF 3 ] 2 , and Pt 2 [ o -(NPh)(N)C 6 H 4 ] 4 Br 2 , have been structurally characterized by single crystal X-ray diffraction studies. The oxidation of complex Pt[ o -(NPh)(N)C 6 H 4 ] 2 by excess AgO 3 SCF 3 afforded a heterotricyclic quinoxaline derivative, whose structure has been determined by X-ray analysis. The data obtained suggest that labile nitrene species coordinated to Pd and Pt complexes are possible intermediates in the reactions under study.

Step-by-step thermal transformations of a new porous coordination polymer [(H{sub 2}O){sub 5}CuBa(Me{sub 2}mal){sub 2}]{sub n} (Me{sub 2}mal{sup 2-}=dimethylmalonate): Thermal degradation to barium cuprate

Abstract The reactions of CuSO4·5H2O, dimethylmalonic acid and Ba(OH)2·H2O (Cu: H2Me2mal: Ba=1: 2: 2) in aqueous and aqueous-ethanol solutions (H2O: EtOH=1: 1) resulted in formation of 3D-porous coordination polymers [(H2O)3(μ-H2O)2CuBa(μ3-Me2mal)(Me2mal)]n (1) and [(μ-H2O)CuBa(μ3-Me2mal)(μ4-Me2mal)]n (2), respectively. It has been shown that compound 2 was an intermediate in the thermal degradation of compound 1. Thorough studies of solid-state thermolysis of 1 and 2 allowed to detect formation of coordination polymer [CuBa(μ4-Me2mal)(μ5-Me2mal)]n (3), structure of which was determined by X-ray powder diffraction. It has been found that the channels in polymer 3 were accessible for guest molecules (MeOH). Theoretical estimation of methanol diffusion barrier was carried out. Complete solid-phase thermolysis of 1 and 2 leads to a mixture of BaCuO2, BaCO3, and CuO. Special conditions for obtaining of a crystalline phase of pure cubic BaCuO2 were determined.

Reactions of pyrrole-2,5-dicarbaldehyde with 2-aminodiphenylamine in the presence of nickel and cobalt trimethylacetates

The reactions of pyrrole-2,5-dicarbaldehyde (1) with 2-aminodiphenylamine (3) taken in a ratio of 1 : 2 in the presence of polinuclear nickel(ii) and cobalt(ii) trimethylacetate complexes were studied in MeCN. The reaction with Ni9(HOOCCMe3)4(μ4-OH)3(μ3-OH)3(OOCCMe3)12 (2) afforded the mononuclear complex Ni(OOCCMe3)2[(PhHN)C6H4NHCHC4H2NCHNC6H4(NHPh)] (4) with a new ligand, which is the product of condensation of one molecule 1 with two molecules 3 and contains two NHPh groups. By contrast, the reaction with the polymeric complex [Co(OH)n(OOCCMe3)2–n]x (5, n = 0.05—0.1) gave rise to the tetranuclear complex Co4(μ4-O)(μ-OOCCMe3)4L2 (6), where L is, apparently, the product of further oxidation of Schiffs base to the benzimidazole derivative. The structures of compounds 4 and 6 were established by X-ray diffraction analysis.