V. V. Sharutin

The palladium complexes [Ph3(cyclo-C3H5)P] 2 + [PdBr4]2−, [Ph3(cyclo-C3H5)P] 2 + [Pd2Br6]2−, and [Ph3(cyclo-C3H5)P]+[PdBr3(DMSO)]−: Synthesis and structures

A reaction of palladium dibromide with HBr and (cyclopropyl)(triphenyl)phosphonium bromide in water followed by recrystallization from acetonitrile or DMF afforded the complexes [Ph3(cyclo-C3H5)P]2+ [PdBr4]2− (I) and [Ph3(cyclo-C3H5)P]]2+ [Pd2Br6]2− (II). Recrystallization of complexes I and II from DMSO gave [Ph3(cyclo-C3H5)P]+[PdBr3(DMSO)]− (III). According to X-ray diffraction data, the P-C bond lengths in the tetrahedral (cyclopropyl)(triphenyl)phosphonium cations of complexes I–III are 1.773(5)–1.802(5) (I), 1.778(5)–1.802(5) (II), 1.767(5)–1.797(5) Å III); the angles CPC are 107.4(2)°–111.1(2)° (I), 107.2(2)°–111.2(2)° (II), and 108.4(2)°–110.5(2)° (III), and (CIF file CCDC no. 999905 (I), 1035313 (II), 999907 (III)). In the square anions [PdBr4]2−, the Pd-Br bond length is 2.4333(5)–2.4459(5) Å. In the planar centrosymmetric dinuclear anions [Pd2Br6]2−, the bond lengths Pd-Brbrid and Pd-Brterm are 2.4559(7), 2.4600(7) and 2.3952(7), 2.4045(8)Å; the angles PdBrPd and BrtermPdBrterm are 92.57(2)° and 91.98(3)°, respectively. In the square anions [PdBr3(DMSO)]−, the DMSO molecule is coordinated by the Pd atom through the sulfur atom (Pd-Br, 2.3986(7)–2.4288(6) Å; Pd-S, 2.2633(13) Å).

Protonation direction of 3-allylthio[1,2,4]triazino[5,6-b]indole and 3-methyl[1,3]thiazolo[3′,2′:2,3][1,2,4]triazino[5,6-b]indole

X-ray diffraction studies have demonstrated that the protonation of 3-allylthio-5H-[1,2,4]triazino-[5,6-b]indole with hydrogen halides occurs at N2 and that of 3-methyl[1,3]thiazolo[3′,2′:2,3][1,2,4]triazino-[5,6-b]indole, at N10.

Tri- and tetraphenylantimony propiolates: Syntheses and structures

The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide (molar ratios 1 : 2 : 1 and 1 : 1 : 1) in diethyl ether affords triphenylantimony dipropiolate Ph3Sb[OC(O)C≡CH]2 (I) and μ2-oxobis[(propiolato)triphenylantimony] [Ph3SbOC(O)C≡CH]2O (II). Tetraphenylantimony propiolate Ph4SbOC(O)C≡CH (III) is synthesized from pentaphenylantimony and propiolic or acetylenedicarboxylic acid in toluene. According to the X-ray diffraction data, the crystals of compounds I and III include two types of crystallographically independent molecules (a and b). The antimony atoms in molecules Ia, Ib, II, IIIa, and IIIb have the trigonal-bipyramidal coordination mode with different degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia, Ib), 170.17(15)°, 178.78(14)° (II), and 173.2(5)°, 174.4(5)° (IIIa, IIIb). The CSbC equatorial angles lie in the ranges 108.2(3)°–143.1(3)° (I), 109.0(2)°–131.0(2)° (II), and 113.1(4)°–125.4(4)° (III). The SbOSb angle in II is 141.55(19)°. The Sb-C bond lengths are 2.103(8)–2.141(5) (I), 2.105(5)–2.119(5) (II), and 2.076(12)–2.166(13) Å (III). The Sb-O distances increase in a series of I, II, and III: 2.139(6)–2.156(7) (Ia, Ib); 2.206(4), 2.218(3) (II); and 2.338(10), 2.340(10) Å (III).

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony bis (cyclopropanecarboxylate)

Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclopropanecarboxylate) I. The structure of the resulting complex was proved by the XRD analysis.

Syntheses and structures of tris(para-tolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony dioximates

Tris(para-tolyl)antimony bis(2-oxybenzaldoximate) (I), tris(para-tolyl)antimony bis(2-nitrobenzaldoximate) (II), tris(para-tolyl)antimony bis(2-bromobenzaldoximate) (III), tris(3-fluorophenyl)antimony bis(2-oxybenzaldoximate) (IV), tris(4-fluorophenyl)antimony bis(2-bromobenzaldoximate) (V), and tris(4-fluorophenyl)antimony bis(2-nitrobenzaldoximate) (VI) are synthesized by the reactions of tris(paratolyl)-, tris(3-fluorophenyl)-, and tris(4-fluorophenyl)antimony with 2-oxy-, 2-nitro-, and 2-bromobenzaldoxime in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in complexes I–VI have a distorted trigonal bipyramidal coordination mode with the oximate ligands in the axial positions. CIF files CCDC nos. 1062231 (I), 1059962 (II), 1465384 (III), 1465109 (IV), 1471948 (V), and 1060387 (VI).

Syntheses and structures of tetraphenylantimony oximates: Ph4SbON=CHR (R = C6H4Br-2, C6H4NO2-2, C4H3S)

The reactions of pentaphenylantimony with oximes or triphenylantimony dioximates in toluene afford tetraphenylantimony oximates Ph4SbON=CHR (R = C6H4Br-2 (I), C6H4NO2-2 (II), and C4H3S-2 (III)). Triphenylantimony dioximates are synthesized by oxidative addition from triphenylantimony and oxime in diethyl ether in the presence of tert-butyl hydroperoxide. According to the X-ray diffraction data (CIF files CCDC no. 1055414 (I), 1055634 (II), and 1061727 (III)), the coordination mode of the antimony atoms in the molecules of compounds I–III is a distorted trigonal bipyramid with the oxygen atom of the oximate ligand in the axial position. The structural organization of the crystals is caused by weak hydrogen bonds.

Tris(para-tolyl)- and tris(4-fluorophenyl)antimony diaroxides: syntheses and structures

Bis(4-bromophenoxy)tris(para-tolyl)antimony (I), bis(4-nitrophenoxy)tris(para-tolyl)antimony (II), bis(4-nitrophenoxy)tris(4-fluorophenyl)antimony (III), bis(2,3,4,5,6-pentafluorophenoxy)tris(4-fluorophenyl) antimony (IV), and bis(2,3,4,5,6-pentachlorophenoxy)tris(4-fluorophenyl)antimony (V) (CIF files CCDC 1470829 (I), 1474589 (II), 1062337 (III), 1470476 (IV), and 1472954 (V)) are synthesized in high yields by the reactions of tris(para-tolyl)- and tris(4-fluorophenyl)antimony with 4-bromo-, 4-nitro-, 2,3,4,5,6-pentafluoro-, and 2,3,4,5,6-pentachlorophenol, respectively, in diethyl ether in the presence of tert-butyl hydroperoxide. The Sb atoms in compounds I–V have a distorted trigonal bipyramidal coordination with the aroxy groups in the axial positions (angles OSbO 174.08(11)°–179.4(5)°). The average Sb–C bond lengths in compounds I–V are similar and independent of the nature of the para-substituent in the aryl rings. The Sb–O distances are close to the sum of covalent radii of Sb and O atoms. Hydrogen bonds H···F are involved in the formation of the crystal structures of compounds III–V.

Synthesis and structure of tetra- and triphenylantimony 2,4,6-trichlorophenoxides

The reaction of pentaphenylantimony with 2,4,6-trichlorophenol or bis(2,4,6-trichlorophenoxy)- triphenylantimony in toluene afforded (2,4,6-trichlorophenoxy)tetraphenylantimony. The reaction of triphenylantimony with tert-butyl hydroperoxide and 2,4,6-trichlorophenol led to the formation of bis(2,4,6-trichlorophenoxy) triphenylantimony; further reaction of the latter with triphenylantimony dichloride provided (2,4,6-trichlorophenoxy)triphenylantimony chloride. According to the XRD data, the antimony atoms in the prepared compounds had distorted trigonal-bipyramidal coordination with electronegative ligands in axial positions.

Reaction of S-allyl and propargyl derivatives of 2-thiouracils with hydrobromic acid

Hydrobromic acid reacts with 2-methallylthio- and 2-prenylthio-4(3Н)-pyrimidinones with participation of the double bond to give the products of heterocyclization, and with 2-allylthio- and 2-propargylthio-6-methyl-4(3Н)-pyrimidinones, with the retention of the double bond and the formation of hydrobromides.

Benzene solvates of tris(4-fluorophenyl)antimony diaryloxides (4-FC6H4)3Sb(OAr)2 • 1/2PhH (Ar = C6H4Cl-4, C6H4Br-4, C6H3Br2-2,4). Synthesis and structure

The solvates of tris(4-fluorophenyl)antimony diaryloxides with benzene, (4-FC6H4)3Sb(OAr)2 • 1/2PhH (Ar = C6H4Cl-4 (I), C6H4Br-4 (II), and C6H3Br2-2,4 (III)), were prepared by the reaction of tris(4-fluorophenyl)antimony with 4-chlorophenol, 4-bromophenol, and 2,4-dibromophenol in diethyl ether in the presence of tert-butyl hydroperoxide followed by recrystallization from a benzene–heptane mixture (2: 1). The antimony atoms in I, II, and III form a distorted trigonal-bipyramidal coordination with oxygen atoms in axial positions (CIF files CCDC nos. 1047500 (I), 1048172 (II), 1048212 (III)). The OSbO angles are 177.23(8)° (I), 177.34(12)° (II), and 179.47(16)° (III). The Sb–O and Sb–C bond lengths are 2.0519(16), 2.0508(18), and 2.105(2)–2.121(2) Å (I); 2.045(3), 2.055(3), and 2.105(4)–2.126(4) Å (II); and 2.066(3), 2.058(3), and 2.100(6)–2.107(5) Å (III). The structural organization in crystals I–III is formed by weak intermolecular C−H•••F hydrogen bonds (H•••F 2.52 Å (I), 2.52 Å (II), and 2.61 and 2.51Å (III)).