Organoantimony compounds. I. Infrared spectra of some trimethyl- and triphenyl-antimony derivatives

Goel, Ram G.; Joshi, P.N.; Ridley, D. R.; Beaumont, R. E.

doi:10.1139/v69-232

Cited by 19 publications

(4 citation statements)

References 2 publications

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“…The other absorption bands which can be assigned to the oxalate group are observed at 1310, 788, and 375 cm-'. The spectrum of the tetraphenylantimony oxalate thus differs significantly with that of triphenylantimony oxalate (17), which shows 2 strong (0-y-0) stretching bands at 1740 and 1655 cm-and for which a 5-coordinate bridging structure is proposed. The oxalate frequencies in tetraphenylantimony oxalate correspond to the presence of either a free oxalate ion or a symmetrical oxalate group functioning as bichelate ligand (18).…”

Section: Table 111mentioning

confidence: 85%

“…The spectral data indeed are in accord with the presence of bridging X groups (1 1, 17). Although in the case of the tetraphenylantimony sulfate only 3 stretching frequencies due to the sulfate group can be assigned with confidence, the spectra of the selenate and the chromate clearly show 4 strong, well resolved bands which can be assigned to the stretching frequencies due to the coordinated selenate or chromate group (11,17). Similarly, in the low frequency region 4 absorption frequencies due to the selenate or chromate group are observed.…”

Section: Molecular Weight and Conductancementioning

confidence: 91%

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Organoantimony compounds. II. Studies on tetraphenylantimony(V) derivatives

Goel¹

1969

Can. J. Chem.

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Tetraphenylantimony halides, pseudohalides, carboxylates, nitrate, sulfate, selenate, and chromate have been synthesized. The infrared spectra, molecular weights, and electrical conductances of these compounds have been investigated to elucidate the chemical constitution. The compounds have molecular, monomeric constitution in benzene solutions. Infrared results indicate that with the exception of the acetate and the oxalate, all the compounds have 5-coordinate structures. The acetate is 6-coordinate in the solid state and 5-coordinate in bromoform or chloroform solution. The oxalate is indicated to be 6-coordinate in the solid state as well as in chloroform solution. The electrical conductivities of the bromide, chloride, thiocyanate, trifluoroacetate, and the nitrate in nitromethane correspond to those of 1 :I electrolyte. The conductivities of the other compounds indicate little dissociation in this solvent.

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Section: Table 111mentioning

confidence: 85%

Section: Molecular Weight and Conductancementioning

confidence: 91%

Organoantimony compounds. II. Studies on tetraphenylantimony(V) derivatives

Goel¹

1969

Can. J. Chem.

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“…Teor. Fiz., 43, 1242 (1962); Sov. Phys.-JETP, 16,879 Additive Model for the efg at Sb. To a first approximation the efg at the 121Sb nucleus can be separated into two terms, a lattice contribution due to charges on the ligands and other ions in the crystal and a valence contribution due to an asymmetric distribution of electrons in bonding and nonbonding valence shell orbitals.27 For highly covalent molecular systems the contribution from external ions is expected to be small and to a good approximation the lattice term arises solely from charges on the ligands.…”

Section: Resultsmentioning

confidence: 99%

Additive model for the electric field gradient at antimony in some pentacoordinate organoantimony(V) derivatives

Ruddick¹,

Sams²,

Scott³

1974

Inorg. Chem.

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to exist as a cubic pyrite structure when prepared and quenched from 800 to 8.50" and as a partially ordered (orthorhombic Pca2, space group) structure when synthesized between 700 and 800"; this partially ordered structure contained ordered As-S pairs. The compounds CoSbS and CoPSe crystallize with an orthorhombic structure, apparently similar to that of cr-NiAsz (pararammelsbergite). CoAsSe and CoSbSe are orthorhombic with the cla and c/b axial ratios of the anomalous marcasite.The temperature-independent magnetic data found for all CoXY materials studied is indicative of low-spin Co3+ (d6).The electrical data for these materials may reflect the specific effect of anions and crystallography on both the broadness and degree of separation of the valence and conduction bands."'Sb Mossbauer data are reported for several compounds of the types Ph,SbX and Ph,SbX, (Ph = C,H,; X = various electronegative groups) and are consistent with trigonal-bipyramidal structures in which the X groups occupy one or both axial positions, respectively. The first explicit application of an additive model for the electric field gradient at Sb in organoantimony(V) compounds has been made to these and other derivatives of like stoichiometries. Calculated and observed quadrupole coupling constants (e'qQ) are in good agreement, indicating the adequacy of such a model for these systems. For compounds of the type Ph,SbX, there is an approximately linear relation between isomer shift ( 6 ) and e'4Q. the slope of which is consistent with o-bonding effects being the dominant factor in determining the Mossbauer parameters. In derivatives containing Sb-0 bonds the S values are more positive than would be expected on the basis of electronegativity arguments alone. AIC30828T IntroductionAdditive models for the electric field gradient (efg) have been extensively employed to interpret Mossbauer quadrupole splitting data on organometallic Sn(1V) derivatives (and to a lesser extent, spin-paired Fe(I1) and Fe(-11) complexes).' Such models have had considerable success in predicting both signs and magnitudes of quadrupole splittings in compounds with fairly regular geometry, although the converse application of predicting molecular geometry from measured efg parameters has met with more limited success. This is due in part to the fact that similar efg parameters may arise from two or more possible structures, so that an unequivocal choice is not always possible. Moreover, no really satisfactory method has yet been devised to account for distortions from regular geometry.In view of the usefulness of the additive approximation for "'Sn quadrupole splittings in organotin(1V) compounds it is obviously of interest to extend the treatment to lZISb quadrupole splittings in organoantimony(V) complexes, since the model should be equally applicable here.la Although ' "Sb Mossbauer results for only a few organoantimony(V) deriva-

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“…In previously reported syntheses, a range of silver salts were used in ion-exchange reactions to form Ph 3 SbCl 2 (Goel et al, 1969) and Ph 4 SbBr (Goel, 1969) derivatives cleanly and in high yields. Our attempts to prepare tellurate(VI) analogues of such compounds led to dearylation and the formation of mixtures.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Tris[triphenylantimony(V)]hexa(μ-oxido)tellurium(VI): a molecular complex with six Te—O—Sb bridges

Domasevitch

Senchyk

2021

Acta Cryst E

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In the structure of the title compound [systematic name hexa-μ-oxido-1:2κ4 O:O;1:3κ4 O:O;1:4κ4 O:O-nonaphenyl-2κ3 C,3κ3 C,4κ3 C-triantimony(V)tellurium(VI)], [Sb3Te(C6H5)9O6], the hexaoxidotellurate(VI) ion is coordinated to three SbV ions via pairs of cis-positioned O atoms to form a discrete molecular unit. The TeVI and SbV central ions exhibit distorted octahedral [TeO6] and distorted trigonal–bipyramidal [SbC3O2] coordination geometries, respectively. The linking of these polyhedra, by sharing the dioxide edges, results in the Te-based octahedron having a mer-configuration. The packing of the molecules is dominated by C—H...O hydrogen bonding and weak dispersion forces, with a minor contribution from C—H...π bonds and π–π stacking interactions. According to the Hirshfeld surface analysis, the contributions of the H...H, H...C/C...H and H...O/O...H contacts are 58.0, 32.6 and 7.8%, respectively. The title structure provides a model for the bonding of triorganoantimony dications to octahedral oxoanions, and the observed doubly bridged motifs, Te(μ-O)2Sb, may find application in the functionalization of polyoxometalate species.

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Organoantimony compounds. I. Infrared spectra of some trimethyl- and triphenyl-antimony derivatives

Cited by 19 publications

References 2 publications

Organoantimony compounds. II. Studies on tetraphenylantimony(V) derivatives

Organoantimony compounds. II. Studies on tetraphenylantimony(V) derivatives

Additive model for the electric field gradient at antimony in some pentacoordinate organoantimony(V) derivatives

Tris[triphenylantimony(V)]hexa(μ-oxido)tellurium(VI): a molecular complex with six Te—O—Sb bridges

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