Investigations on organoantimony compounds

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 hav…

Complexes of Tin(IV) with Tridentate Ligands M�SSBAUER, Infrared, and Solution Phase Studies

The configuration in the solid state and in solution phase of complexes of SuIV wit,li tridentate “planar” ligands, Sn(trid)2 and HNEt3Cl3 Sntrid, have been investigated by infrared and MOSSBAUER spectroscopy, as well as by osmometry, conductivity, and electronic and PMR spectroscopy. The presence of monomeric Sn(trid)2 and ionic [HNEt] [Cl3Sn trid−] species has been inferred. Octahedral type configurations are advanced for both classes of compounds. Komplexe des Zinn (IV) mit dreizahigen Liganden. Mossbauer- und IR-Spektren sowie Untersuchungen von Losungen Die Struktur von SnIV-Komplexen mit dreizahnigen “planaren” Liganden, Sn(trid)2 und HNEt3Cl2Sntrid, wurde in fester Phase und in Losun…

Infrared and M�SSBAUER spectroscopic studies on complexes of Hal2SnIV moieties with tridentate ligands

Novel complexes hal2Sntrid, where hal Cl, Br, and trid2− are dianions of „planar” tridentate ligands with ONO and SNO donor basic atoms, were synthesized and structurally investigated in the solid state mainly by far infrared and MOSSBAUER spectroscopy. Possible configurations were advanced and discussed, and it was concluded that the most probable is a monomeric trigonal bipyramidal structure for all compounds, although polymers, or dimers with O or Cl bridges, were not a priori excluded, in a special way for Br2Sntrid. Infrarot- und MOSSBAUER-spektroskopische Untersuchungen an Komplexen von Hal2SnIV mit dreizahnigen Liganden Neue Komplexverbindungen von Typ hal2Sntrid werden dargestellt (…

Solution structure of R2Sn(IV)-β-N-Acetyl-Neuraminate (R=Me, Bu) complexes in D2O and DMSO-d6: experimental NMR and DFT computational study.

Two diorganotin(IV)-NANA complexes (NANA (1) = beta-N-acetyl-Neuraminic Acid = 5-amino-3,5-dideoxy-D-glycero-beta-D-galactononulosic acid) with formula Me(2)Sn(iv)NANA (2) and Bu(2)Sn(IV)NANA (3) were synthesized and characterized by (1)H, (13)C and (119)Sn NMR spectroscopy, both in D(2)O and DMSO-d(6) solutions. The experimental data in DMSO suggested the monosaccharide bidentate chelation via O1 carboxylate and vicinal O2 alkoxide atoms, which, in D(2)O, can be dynamically extended to a third binding site (O8 atom) of the pendant chain. Coordination at the tin atom is discussed on the basis of experimental NMR data and DFT calculation.

Synthesis and characterization of mixed catecholate and 1,10-phenanthroline complexes of antimony(III), C6H4O2SbX·1,10-phenanthroline (X  F, Cl, Br, I)

Abstract The title compounds have been easily synthesized by reacting antimony(III) catecholates, C 6 H 4 O 2 SbX, with 1,10-phenanthroline. The infrared spectra of the solids are in accordance with a chelating behaviour of the phenanthroline ligand and the molecular monomeric nature of the fluoride derivative. In the case of the chloride, and possibly also for X  Br and I, infrared data are better interpreted admitting a consistent ionic SbX bond interaction. The conductance data for their methanolic solutions also indicate a distinctive behaviour of the fluoride derivative, this being weakly ionized, whereas the remaining halides behave as 1:1 electrolytes. The main features of the mass…

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.

Complexes of organometallic compounds

Abstract Several new complexes formed by PhTlCl 2 with tridentate ligands (with ONO and SNO donor atoms) and a tetradentate ligand (with ONNO donor atoms), have been prepared. The complexes show 1/1 organothallium(lll)/Ligand ( = L 2− ) stoichiometry. Their nature and configuration are investigated in the solid state by vibrational spectroscopy, and in solution by electronic spectroscopy. The existence of chelation by the dianionic ligands on Tl III is inferred, and suggestions are made concerning the Tl III coordination number and the stereochemistry of the complexes.

119Sn NMR Ccomputational study of Dimethyltin(IV) - D-ribonic Acid and Dimethyltin(IV) - N-Acetylneuraminic acid complexes

Arsenic, antimony and bismuth complexation by L-cysteine in water

Synthese, dans l'eau, des complexes L-cysteine: AsL 3 , SbL 3 •H 2 O et BiL 3 .H 2 O L=forme monoanionique de cysteine. Etude IR des structures

Organotin(IV) azido and mixed azidothiocyanato complex anions; A Mössbauer and vibrational spectroscopic study

Abstract Tetraphenylarsonium and tetramethylammonium salts of the complex anions Ph 3 Sn(N 3 ) − 2 , Ph 3 Sn(N 3 )(NCS) − , Me 2 Sn(N 3 ) 2− 4 and Ph 2 Sn(N 3 ) 2 (NCS) 2− 2 have been synthesized, and the solid state configuration of the complex anions has been studied by Mossbauer and vibrational spectroscopies. Trigonal bipyramidal structures are advanced for the Ph 3 Sn IV derivatives, with equatorial SnC 3 and apical pseudohalide ligands, while the R 2 Sn IV compounds are assumed to be trans -octahedral species. The NCS − ligands are observed to be N-bonded to Sn IV . Conductance and PMR (for the Me 2 Sn IV compound) data suggest the presence of the complex anions also in solution phase…

Recent Results of Studies on Dialkyltin(IV) Complexes of Acidic Derivatives of Carbohydrates

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.

Mössbauer studies on tin(IV) and organotin(IV) diacetylbis(benzoylhydrazone) complexes

Abstract The Mossbauer parameters of Ph 2 SnDB, PhClSnDB and Sn(DB) 2 were determined, where DB 2− is the dianion of the multidentate ligand diacetylbis(benzoylhydrazone). According also to data treatment with the point charge model formalism, the configurations of Ph 2 Sn IV and PhSn IV derivatives appear to be essentially octahedral, with linear CSnC and CSnCl skeletons. As to Sn(DB) 2 , it appears that the electrical charge density at the Sn IV nucleus has a cubic symmetry, which is consistent with both tetrahedral and octahedral configurations around Sn IV .

Infrared and Mössbauer studies on adducts R3SnOH · R3MX (M = Sn, Pb; X = Pseudohalide)

Abstract The synthesis of the solid adducts Me3SnOH · Me3 SnNCO, Me3SnOH · Me3SnNCS, Me3SnOH · Me3PbN3, Ph3SnOH · Ph3SnN3 is reported. The compounds have been investigated by infrared and Mossbauer spectroscopy. Their structure probably consists of polymeric OH-R3Sn-X-R3Sn(Pb) chains in which hydroxyl and pseudohalide (X) groups are bridging pentacoordinate tin atoms. In contrast to the triphenyl compound, the trimethyl derivatives show evidence of hydrogen bonding between adjacent chains.

Antimony-121 mössbauer and infrared spectral study on halophenylantimonate(III) Compounds

Abstract The synthesis and the 121 Sb Mossbauer and infrared spectra of halophenylantimonates(III) M[PhSbX 3 ] (M  Me 4 N, Ph 4 As;X  Cl, Br, I) are reported, and the spectral data are discussed and compared with those of SbX 4 and other related systems. The results are in accord with the participation of the antimony 5s electrons in the SbPh bond. In the interpretation of the electric field gradient, the contributions to V zz from both the lone pair and the SbPh bond electron densities are assumed to be dominant.

Studies on some antimony(III) complexes with tridentate schiff base ligands

Abstract The antimony(III) complexes FSb(Sab), ClSb(Sab) and ClSb(Sat) containing dianonic, potentially tridentate Schiff-base ligands with ONO(Sab 2− ) and ONS(Sat 2− ) donor atoms have been prepared and characterized. The mass spectra of these derivatives are reported. The occurrence of chelation by the tridentate ligand is inferred from the infrared data. The antimony-121 Mossbauer parameters at 4.2 K are reported. The magnitudes and the positive sign of eQV zz suggest a consistent p-character of the antimony lone-pair orbital. Observed differencies in the isomer shift and eQV zz values are discussed on the basis of the likely distribution of electron density around antimony.

In search of layered antimony(III) materials: synthesis and characterization of oxo-antimony(III) catecholate and further studies on antimony(III) phosphate

Abstract A new layered oxo-antimony(III) catecholate, [Sb(C6H4O2)]2O, can be obtained by reacting senarmontite with aqueous catechol. The same reaction performed with valentinite, the other allotropic form of Sb2O3, shows an intermediate hydrate that loses water at about 100°C. Both compounds can be obtained from SbPO4 under appropriate experimental conditions. [Sb(C6H4O2)]2O and the hydrated form, which appear to be layered materials, have been characterized by X-ray diffraction, thermogravimetric/differential thermal analyses, and infrared techniques. Preliminary evidence of a reversible intercalation of pyridine into [Sb(C6H4O2)]2O was collected. Taking into consideration the possible us…

Synthesis and structural investigations on R2Sn(IV)-D-aldonic acid complexes (R = methyl; butyl). Their effect on a new toxicity test organism,Liza saliens(Osteichthyes, Mugilidae): a histological study

Eight R2Sn(IV)-D-aldonate complexes [(R = Me, Bu; D-aldonate = D-galactonate2− (Galn), D-Gluconate2− (Glun), D-Gulonate2− (Guln), D-Ribonate2− (Ribn)], five of which are new derivatives, have been synthesized and structurally characterized both in solid and solution state by IR, 119Sn Mossbauer and 1H, 13C, 119Sn NMR spectroscopies, showing that ligands act as dianonic chelating agents. In solution phase, NMR data suggest that the bidentate chelation is attained by the O1 carboxylate and the vicinal O2 alkoxide atoms, which can be dynamically extended to a third binding site (O4) competing with O2. In Me2Sn(IV)-D-gluconate complex the occurrence of a self-association process leading to a di…

Complexes of organometallic compounds

Abstract Tetraphenylarsonium and tetramethylammonium salts of the complex anions Ph 3 Pb(N 3 ) − 2 , Ph 3 Pb(N 3 )(NCS) − , Ph 2 Pb(N 3 ( 2 − 4 )) and Ph 2 Pb(N 3 )(NCS) − 2 have been prepared and characterized. Infrared spectra and solution conductance data are reported. Possible configurations of the complex anions are discussed.

On the synthesis and characterization of layered antimony(III) phosphate and its interaction with moist ammonia and amines

Samples of antimony(III) phosphate, a layered material, were prepared at room temperature, using the two allotropic forms of Sb2O3, layered valentinite and cubic senarmontite. The compounds were characterized by infrared spectroscopy, X-ray diffraction, and thermogravimetric–differential thermal analysis. Solids exposed to ammonia, ethylenediamine, or hydrazine vapors also were studied. The interaction between SbPO4 and the bases always led to the formation of stoichiometric amounts of Sb2O3 and hydrogen phosphate(–2) salts of the bases. With ammonia, the SbPO4 raw materials gave rise to valentinite or senarmontite, depending on which Sb2O3 allotropic form was used to prepare antimony phosp…

Preparation, crystal structure, and infrared characterization of the first thiocyanato-oxy-antimonate(III) [(CH3)4N]2[Sb6O4(NCS)12]

The salt [(CH3)4N]2[Sb6O4(NCS)12] is the first identified thiocyanato-oxy-antimonate(III) complex. Reported are details of the synthesis, relevant infrared data and its x-ray structure. The compound crystallizes in the triclinic space group P1 with Z = 2 (C10H12N7O2S6Sb3) and unit cell dimensions a = 11.314(6), b = 12.846(3), c = 8.679(2) A; α = 91.93(3)°, β = 90.31(3)° and γ = 99.13(3)°. It contains centrosymmetric [Sb6O4(NCS)12]2− anions packed with isolated tetramethyl-ammonium cations. The fundamental structural element of the anion is provided by the fusion of three SbOSbO rings forming a zig-zag portion of a ribbon, only slightly pleated. Peculiar is the unequivalence of the six thioc…

Complexes of dichlorophenyl and trichloro-antimony(V) moieties with dianionic tridentate ligands

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.

Recent results on DFT calculation of 119Sn NMR parameters for organotin(IV) derivatives in coordinating solvents

Complexes of organometallic 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.

Mössbauer spectroscopic studies on compounds containing tin-cadmium and tin-zinc bonds

The Mossbauer parameters of compounds Ph3Sn MCl · TMED (M = Cd, Zn; TMED = N,N,N′,N′-tetramethylethylenediamine), (Ph3Sn)2CdL2 (L2 = TMED, 2,2′-bipyridine and o-phenanthroline) and (Ph3Sn)2 Zn · TMED have been determined and are discussed in connection with Mossbauer data concerning Ph3SnIV derivatives with other Sn-metal bonds. The isomer shift values suggest a high s character in SnCd and SnZn bonds resulting in deviations from regular tetrahedral environments around tin. Experimental quadrupole splittings and calculated partial quadrupole splitting values indicate reduced donor abilities towards the tin atom of an individual Ph3SnIV moiety by Cd-and Zn(Ph3Sn)1−nClnL2 (i.e., the remaini…

Antimony-121 Mössbauer and infrared spectral studies on 1,10-phenanthroline adducts of antimony(III) halides

Abstract The syntheses of the mono-adducts of 1,10-phenanthroline with SbX 3 (X = F, Cl, Br) and PhSbI 2 are described. These compounds and the 1:1 adduct between 2,2′-bipyridine and PhSbI 2 have been characterized mainly in the solid state by infrared and Mossbauer spectroscopic techniques. The structures of the antimony trihalide complexes appear to be based on halogen bridged polymers in which the stereochemical activity of the lone pair of electrons varies with the halogen, the highest p-character of the lone pair being observed with the trifluoride adduct. Mossbauer results for the PhSbI 2 complexes suggest a ψ-octahedral stereochemistry with the lone pair and the Ph group in trans pos…

Diorganotin(IV) complexes with aldonic acids. Synthesis and structural study in solid state and in solution phase and biological activity

Tetramethylammonium chlorodiphenylthiocyanatoantimonate(III)

The crystal structure of the title compound, (C4H12N)[Sb(C6H5)2Cl(NCS)], contains two cations and two anions in the asymmetric unit. The Sb atom exhibits a distorted pseudo-trigonal–bipyramidal coordination, with the phenyl groups and the lone pair of electrons in equatorial positions and N-bonded thio­cyanate and Cl− ligands in axial positions.

Diorganotin(IV) complexes ofD-galacturonic acid: solid-state and solution-phase structural study

Three diorganotin(IV) complexes of D-galacturonic acid (H2GalA; R = Me, n-Bu, Ph), two of which are new derivatives (R = Me, Ph), have been synthesized and their solid-state and solution-phase investigated by IR, Mossbauer, 1H, 13C and 119Sn NMR spectroscopy. The FTIR data suggest that H2GalA, in the dialkyltin derivatives, behaves as a dianionic ligand, coordinating the tin(IV) atom through an ester-type carboxylate and deprotonated alcoholic hydroxo groups, whereas a bridging carboxylate occurs in the diphenyltin(IV) complex. Octahedral and trigonal bipyramidal local geometries on tin(IV) atoms are proposed for dialkyltin(IV)GalA and diphenyltin(IV)GalA complexes respectively on the basis…

Synthesis and crystal structure of [(PhenH)(PhenH2)][BiCl6] . 2H2O with different o-phenanthroline protonations.

The reaction between bismuthate oxide and phen (1,10-phenanthroline) in acid medium led to the isolation of the unusual [(PhenH)(PhenH2)][BiCl6] 2H2O derivative, which has been characterized by X-ray analysis and IR spectroscopy. The compound crystallizes in the triclinic space group P1 with a = 8.313(2), b = 9.349(2), c = 9.807(3) A, a = 86.39(3), B = 110.27(3) and y = 106.48(3)°. The crystal structure is made of [BiCl6] 3- anions and [(PhenHXPhenr2)]3+cations. A network of hydrogen bond interactions involving the two clathrated water molecules, the phenanthroline moiety and the chlorines characterizes the entire structure.

Investigations on organoantimony compounds

Abstract Diorganoantimony(V) complexes of the type R 2 SbClTrid (R = Me, Ph) containing dianionic, potentially tridentate Schiff-base ligands with ONO donor atoms (Trid 2− ) have been prepared and characterized. IR and NMR data suggest an octahedral coordination environment for the antimony atom with meridional arrangement of the ONO ligand atoms and a linear CSbC skeleton.

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 …

Investigations with ion-exchange papers

SYNTHESIS, LASER-RAMAN, INFRARED AND PROTON MAGNETIC RESONANCE SPECTRA OF (CH3)3PtX2- 3 IONS (X = Cl−, Br−) AND (CH3)3Ptiv ISOCYANIDE COMPLEXES

Abstract The novel ionic complexes [(C6H5)4As]2 [(CH3)3PtX3](X = Cl− and Br−) and [(CH3)3Pt(bipy)L]+[B(C6H5)4]− (bipy = 2,2′-bipyridine, L = aliphatic and aromatic isocyanide) have been prepared. The structure of the complex ions has been inferred from Laser-Raman and infrared spectra in the solid state and 1H NMR in solution. These data are consistent with a facial configuration of the organometallic moiety. Trends in vibrational frequencies ν(Pt-C) and ν(Pt-X) indicate a “trans” influence sequence for the ligands, which in the case of (CH3)3PtX2- 3 is related with that found for (CH3)2AuX− 2 ions.

Synthesis, antimony-121 mössbauer and infrared spectral characterization of antimony trifluoride and catecholatoantimony(III) fluoride adducts with tridentate nitrogen donors

Abstract The synthesis of the adducts SbF 3 (L) and (C 6 H 4 O 2 )SbF(L) [L = pyridine-2-carboxaldehyde- 2-pyridylhydrazone (paphyH); 2,2′:6′,2″-terpyridine (terpy) and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tpta)] is reported. Infrared data are consistent with the occurred chelation from the terdentate ligand providing an overall pseudo-seven coordination at Sb. The stereoactivity of the antimony lone pair is inferred from the large value of the Mossbauer quadrupole coupling constant observed for all the compounds.

An infrared study of organothallium thiocyanates

Abstract Some structural aspects of the organothallium(III) thiocyanates R 2 TlCNS (R = Me, Ph).[Ph 4 As][Me 2 Tl(CNS) 2 ] and Phtl(CNS) 2 have been studied by IR spectroscopy. From the frequencies of the NCS group vibrations in the solids, and the integrated intensity of the C≡N stretching absorption in solution, it was ascertained that the diorganothallium derivatives are isothiocyanates with a certain amount of ionic character in the TlNCS bonds, whereas PhTl(CNS), is essentially a TlSCN bonded compound. Apparently both solid Me 2 TlCNS and [Ph 4 As][Me 2 Tl(CNS) 2 ] do not show IR active ν s (TlC 2 )bands. The compound Me 2 TlCNS displays a double ν as (TlC 2 band, from which the pres…

Complexes of (CH3)2AuIII: synthesis, PMR and IR spectra

Abstract The syntheses and reactivity of dimethylgold(III) complexes with multidentate ligands as TRIPHOS (i.e., 1,1,1-tris(diphenylphosphinomethyl)ethane) and TREN (i.e. 2,2′,2″-triaminotriethylamine) have been examined. I.r. spectra for the compounds in the solid state, conductivity and PMR data for solutions, lead to the assignment of an ionic formula [CH 3 ) 2 Au TRIPHOS] + [(CH 3 ) 2 AuCl 2 ] − where the gold(III) atoms are presumably four-coordinate. The complex (CH 3 ) 2 AuCl TREN in DMSO solution undergoes a reductive elimination reaction, as found for analogous dimethylgold(III) derivatives.