N. Bertazzi

The influence of aromatic cations on the geometries of the Bi(III) halide polyhedra. Synthesis and crystal structures of quinolinium, isoquinolinium and 8-hydroxyquinolinium polychlorobismuthate(III) derivatives

Abstract The compounds [quinolinium]4[Bi2Cl10] (1), [isoquinolinium]4[Bi2Cl10].2H2O (2) and [8-hydroxyquinolinium]4[BiCl6]·Cl·2H2O (3) have been obtained by reacting bismuthate oxide and the appropriate base in HCl acid medium. The crystal structures of 1 and 2 consist of quinolinium and isoquinolinium cations, respectively, interacting through hydrogen bonding with [Bi2Cl10]4− dimers. The different degree of interactions in the two derivatives causes significant differences in the bond distances of the anions. The crystal structure of 3 is made of [BiCl6]3− and Cl− anions and 8-hydroxyquinolinium cations. Hydrogen bond interactions including the N-bonded and O-bonded H atoms together with an interstitial chlorine atom stabilize the entire crystal structure.

Synthesis and low-frequency vibrational spectra of some halo- and pseudohalo-diphenylantimonates(V)

Abstract The syntheses of diphenylantimonates(V) of the type M(I) [PH 2 XbX 4 ] (M(I) = PH 4 As; X = F, Cl, Br, N 3 , NCS; X 4 = Cl 3 Br, Cl 3 N 3 ) are described. Far-Ir spectra of these compounds and of previously synthesized M(I) [Ph 2 SbCl 3 X] species (M(I) = Me 4 N; X = Cl, Br, N 3 ; M(I) = Ph 4 As; X = NCS) are reported. Raman spectra of tetrafluoro and tetrachloro salts are also given. Vibrational data are interpreted in terms of the presence of solid of trans -Ph 2 SbX 4 - species and assignments of skeletal modes are suggested.

Complexes of organometallic compounds : XXXI. Studies on organolead(IV) thiocyanate compounds

Abstract The configurations of (CH 3 ) 3 PbNCS, (C 6 H 5 ) 3 PbNCS, (C 6 H 5 ) 2 Pb(NCS) 2 , (C 6 H 5 ) 3 Pb(NCS) 2 − and (C 6 H 5 ) 2 Pb(NCS) 4 2− have been investigated in the solid and (except for the insoluble diphenyl derivative) in solution. From infrared spectroscopy it is deduced that the compounds are isothiocyanates in both states, and there is evidence for a polymeric nature of the solid neutral species involving bridging through NCS. PMR and osmometric investigations show that five-coordinate species (CH 3 ) 3 Pb(NCS)·(CH 3 ) 2 CO are present in acetone solution. Possible configurations are discussed.

X-ray crystal structure and antimony-121 Mössbauer spectrum of catecholato bis(1,10-phenanthroline)antimony(III) tetraphenylborate

The crystal structure of the title compound was solved by means of X-ray diffraction at room temperature. The salt consists of a tetrahedral tetraphenylborate anion and a complex cation containing a catecholatoantimony(III) unit chelated by two 1,10-phenanthrolines. The three bidentate ligands are essentially arranged in one half of the Sb coordination sphere, leaving ample space to accomodate the lone pair of electrons. The Mossbauer parameters of the title compound and of the complex (C6H4O2)SbF·Phen were measured and their rationalization accomplished in the light of their respective molecular structures.

Bismuth trihalide complexes with nitrogen and phosphorus chelating ligands

Abstract Bismuth(III) halides react with 1,10-phenanthroline, 2-pyridinecarboxaldehyde-2-pyridylhydrazone and diphenylphosphynoethane in methanol. A stoichiometry differing from 1:1 is found only for BiCl 3 (Phen) 1.33 and BiCl 3 (Dpe) 1.5 . Characterization of these compounds, which are not very soluble in common solvents, follows from analytical, mass and IR spectral data. In the low frequency region, the IR spectra proved to be useful to ascertain the presence of bridging halogens.

Investigations on organoantimony compounds: XVI. Preparation and properties of heterocyclic trichloro-cis-diorganoantimony(V) compounds and of the corresponding tetramethylammonium tetrachlorodiorganoantimonates

Abstract Trichlorodiorganoantimony(V) compounds, R2SbCl3, in which the antimony atom is part of a heterocyclic ring have been synthesized. They have been converted into the corresponding tetramethylammonium tetrachlorodiorganoantimonates, [R2SbCl4]− [Me4N]+, which are hexacoordinate diorganoantimony(V) species in which the antimony-carbon bonds are forced into a cis-position. 5,5,5-Trichlorodibenzostibole, 10,10,10-trichlorophenoxantimonin, 5,5,5-trichloro-5,10-dihydrodibenz[b, e]antimonin and 5,5,5-trichloro-10,11-dihydro-5H-dibenzo[b, f]stibepin have been prepared by chlorination of the corresponding heterocyclic chlorodiarylstibines. Heterocyclic trichlorodialkylantimony(V) compounds have been prepared by a reaction sequence involving the chlorination of the corresponding heterocyclic distibines. Treatment of 1-methylstibolane (1-methylstibacyclopentane) or 1-methylantimonane (1-methylstibacyclohexane) with sodium in liquid ammonia results in the almost exclusive cleavage of the antimony-methyl carbon bond to give sodium antimonides, which on treatment with 1,2-dichloroethane give the corresponding heterocyclic distibines, 1,1′-bistibolane and 1,1′-biantimonane. Upon treatment with sulphuryl chloride in a 1 3 molar ratio these heterocyclic distibines give 1,1,1-trichlorostibolane and 1,1,1-trichloroantimonane, respectively. The trivalent heterocyclic monochlorostibines 1-chlorostibolane and 1-chloroantimonane have been prepared analogously by reaction of the corresponding distibines with sulphuryl chloride in a 1 1 molar ratio. Complexes of the types [cis-R2SbCl4]− [Me4N]+ were readily obtained from the 1 1 reaction of compounds cis-R2SbCl3 with tetramethylammonium chloride, but the seven-membered heterocyclic antimony compound 5,5,5-trichloro-10,11-dihydro-5H-dibenzo[b, f]stibepin is unreactive because of steric hindrance around the antimony atom. The complexes [(CH2)nSbCl4]− [Me4N]+ (n = 4, 5) decompose slowly in methanol with formation of [Sb2Cl9]3− [Me4N]3+. IR data of the various compounds are reported.

Synthesis and crystal structures of 4,4′-bipyridinium and 2,2′-bipyridinium pentachloro complexes containing the polynuclear anions [Bi2Cl10]4− and [Bi4Cl20]8−

AbstractThe compounds 4,4′-bipyridinium(2+) pentachloro-bismuthate(III) (1), [4,4′-(C10H8N2)BiCl5] and 2,2′-bipyridinium(2+) pentachloro-bismuthate(III) (2), [2,2′-(C10H8N2)Bi2Cl10] have been obtained by reacting bismuthate oxide and 4,4′-bipyridine or 2,2′-bipyridine in HCl acid medium. They have been characterized by single crystal X-ray analysis. (1) crystallizes in the triclinic space group

Complexes of organometallic compounds : XLIII. Synthesis and infrared spectra of fluoro-, chloro- and bromo-phenylantimonates(V)

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