Thiobenzoates of lead (II) and bismuth (III). The crystal and molecular structures of (AsPh4) [Pb(SOCPh)3] and Pb(SOCPh)2(S2CP{c-C6H11}3)

Burnett, Thomas R.; Dean, Philip A. W.; Vittal, Jagadese J.

doi:10.1139/v94-144

Cited by 32 publications

(19 citation statements)

References 13 publications

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“…for the (Ph 4 As)[Pb(SOCPh) 3 ] complex with PbS 3 O 3 coordination (δ Pb = 1422 – 1463 ppm). 57 The resemblance of our reported isotropic chemical shift (δ iso = 2105 ppm) for the crystalline bis (2-aminoethanethiolato)lead(II) complex, Pb( S,N -aet) 2 , to the 207 Pb NMR chemical shifts observed for our alkaline Pb(II) cysteine solutions, further supports the proposed 4-coordinated structure for the [Pb( S,N -Cys) 2 ] 2− complex.…”

Section: Resultssupporting

confidence: 77%

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

et al. 2015

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The lead(II) complexes formed with the multidentate chelator L-cysteine (H2Cys) in alkaline aqueous solution were studied using 207Pb, 13C and 1H NMR, Pb LIII-edge X-ray absorption and UV-vis. spectroscopic techniques, complemented by electro-spray ion mass spectrometry (ESI-MS). The H2Cys/Pb(II) mole ratios were varied from 2.1 to 10.0 for two sets of solutions with CPb(II) = 0.01 and 0.1 M, respectively, prepared at pH values (9.1 – 10.4) for which precipitates of Pb(II)-cysteine dissolved. At low H2Cys/Pb(II) mole ratios (2.1 – 3.0) a mixture of the dithiolate [Pb(S,N-Cys)2]2− and [Pb(S,N,O-Cys)(S-HCys)]− complexes with the average Pb-(N/O) and Pb-S distances 2.42 ± 0.04 Å and 2.64 ± 0.04 Å, respectively, was found to dominate. At high concentration of free cysteinate (> 0.7 M) a significant amount converts to the trithiolate [Pb(S,N-Cys)(S-HCys)2]2−, including a minor amount of a PbS3 coordinated [Pb(S-HCys)3]− complex. The coordination mode was evaluated by fitting linear combinations of EXAFS oscillations to the experimental spectra, and by the 207Pb NMR signals in the chemical shift range δPb = 2006 – 2507 ppm, which became increasingly deshielded with increasing free cysteinate concentration. One-pulse magic angle spinning (MAS) 207Pb NMR spectra of crystalline Pb(aet)2 (Haet = 2-aminoethanethiol or cysteamine) with PbS2N2 coordination were measured for comparison (δiso = 2105 ppm). The UV-vis. spectra displayed absorption maxima at 298 – 300 nm (S− → PbII charge transfer) for the dithiolate PbS2N(N/O) species; with increasing ligand excess a shoulder appeared at ∼ 330 nm for the trithiolate PbS3N and PbS3 (minor) complexes. The results provide spectroscopic fingerprints for structural models for Pb(II) coordination modes to proteins and enzymes.

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Section: Resultssupporting

confidence: 77%

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

et al. 2015

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“…This isotropic chemical shift is considerably upfield, relative to the reported chemical shifts for PbS 3 O 3 coordination. 55 Earlier reports suggest that an increase in the coordination number increases the shielding on the Pb(II) ion. 46 , 56 …”

Section: Resultsmentioning

confidence: 99%

Lead(II) Binding to the Chelating Agent d-Penicillamine in Aqueous Solution

et al. 2014

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A spectroscopic investigation of the complexes formed between the Pb(II) ion and D-penicillamine (H2Pen), a chelating agent used in the treatment of lead poisoning, was carried out on two sets of alkaline aqueous solutions with CPb(II) ≈ 10 and 100 mM, varying the H2Pen/Pb(II) mole ratio (2.0, 3.0, 4.0, 10.0). UV-vis. spectra of the 10 mM Pb(II) solutions consistently showed an absorption peak at 298 nm for S− → Pb(II) ligand-to-metal charge-transfer. The downfield 13C NMR chemical shift for the penicillamine COO− group confirmed Pb(II) coordination. The 207Pb NMR chemical shifts were confined to a narrow range between 1806 and 1873 ppm for all Pb(II)-penicillamine solutions, indicating only small variations in the speciation even in large penicillamine excess. Those chemical shifts are considerably deshielded relative to the solid-state 207Pb NMR isotropic chemical shift of 909 ppm obtained for crystalline penicillaminatolead(II) with Pb(S,N,O-Pen) coordination. The Pb LIII-edge extended X-ray absorption fine structure (EXAFS) spectra obtained for these solutions were well modeled with two Pb-S and two Pb-(N/O) bonds with mean distances 2.64 ± 0.04 Å and 2.45 ± 0.04 Å, respectively. The combined spectroscopic results, reporting δ(207Pb) ~1870 ppm and λmax ~ 298 nm for a PbIIS2NO site, are consistent with a dominating 1:2 lead(II):penicillamine complex with [Pb(S,N,O-Pen)(S-HnPen)]2−n (n = 0 – 1) coordination in alkaline solutions, and provide useful structural information on how penicillamine can function as an antidote against lead toxicity in-vivo.

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“…(1). Very recently the synthesis of Bi(SOCPh)3 was also reported from the reaction of Bi(OAc)3/Bi(SPh)3 with thiobenzoic acid [5]. …”

Section: Resultsmentioning

confidence: 99%

“…The monothiocarboxylates can be classified as asymetrical sulfur ligands [2] with the potential of bind ing metal ions depending upon their hardness and softness. Surprisingly, few metal thiocarboxylates [3 -5 ] have been prepared so far and even fewer ones [5][6][7][8][9] have been examined for structural de tails. Amongst group 15 elements, there are two reports on the structures of thioacetate complexes.…”

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confidence: 99%

Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)₃ and PhSb(SOCPh)₂

Singh

Gupta

et al. 1998

Zeitschrift Für Naturforschung B

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Tris-thiobenzoates, Arsenic, Antimony, BismuthTris-thiobenzoates o f arsenic, antimony and bismuth, M(SOCR)3 have been obtained from their oxides and characterized. In the X-ray crystal structure determinations of these, the group 15 atom and the three covalently bonded sulfur atoms are found to constitute a trigonal pyramid, the central atoms lie at a C3 axis. In the bismuth complex the thiobenzoate ligand tends to chelate. However, three comparatively short intermolecular M---S interactions are significant features for these molecules resulting in stacking of trigonal prisms providing an essentially six coordinate environment around arsenic and antimony and a nine-coordinate one for bismuth. The structure of PhSb(SOCPh)2 can be considered Metal carboxylates [1] are known to display in teresting structural features arising from the varying modes of bonding of the carboxylate anions. The monothiocarboxylates can be classified as asymetrical sulfur ligands [2] with the potential of bind ing metal ions depending upon their hardness and softness. Surprisingly, few metal thiocarboxylates [3 -5 ] have been prepared so far and even fewer ones [5-9] have been examined for structural de tails. Amongst group 15 elements, there are two reports on the structures of thioacetate complexes. In antimony tris-thioacetate [10] antimony is found to possess eight-fold coordination, and the resultant geometry is best described as a distorted dodeca hedron. A bidentate bonding pattern of the thioac etate group is also present in phenylantimony bisthioacetate [11] whose geometry is o f a distorted square-pyramidal shape.Our systematic efforts in main group metal com plexes of asymmetrical sulfur ligands such as thio-ß-diketonate [12-16] and thiocarbamate [17][18][19][20][21][22][23][24][25][26][27][28][29] have provided many discernible and interesting structural features. Thiocarboxylates are the natu ral extension of this thematic approach [8], and we report here on the synthesis and structure of the trismonothiobenzoates o f arsenic, antimony and bis muth as well as of PhSb(SOCPh)2.* Reprint requests to Dr. V. D. Gupta or Prof. H. Nöth.to be distorted trigonal bipyramidal. ExperimentalAll experiments were carried out under anhydrous conditions. Solvents were purified and dried by stan dard methods. Arsenic, antimony and bismuth oxides (Fluka) were used without further purification. PhSbCb and PhaSbCl were prepared by literature methods [21], as well as monothiobenzoic acid (b. p. 85 -87 °C/10 mm Hg) and potassium thiobenzoate [22], Sulfur was estimated by Messenger's method. IR spectra were recorded in the re gion 4000-400 cm-1 on a JASCO FT/IR-5300 spectrom eter on KBr disks. Elemental analyses were carried out on a Perkin-Elmer 240C model analyzer. NM R spectra were recorded in CDC13 using SiMe4 as an internal reference on a JEOL 270 spectrometer.Preparation o f compounds 1 -3 (Table I ) A solution of the respective thiobenzoic acid in dichloromethane (~ 20 cm3) in appropriate molar ra tio was added dropwise with constant stirri...

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Thiobenzoates of lead (II) and bismuth (III). The crystal and molecular structures of (AsPh₄) [Pb(SOCPh)₃] and Pb(SOCPh)₂(S₂CP{c-C₆H₁₁}₃)

Cited by 32 publications

References 13 publications

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

Lead(II) Binding to the Chelating Agent d-Penicillamine in Aqueous Solution

Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)₃ and PhSb(SOCPh)₂

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Thiobenzoates of lead (II) and bismuth (III). The crystal and molecular structures of (AsPh4) [Pb(SOCPh)3] and Pb(SOCPh)2(S2CP{c-C6H11}3)

Cited by 32 publications

References 13 publications

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

Lead(II) Complex Formation with l-Cysteine in Aqueous Solution

Lead(II) Binding to the Chelating Agent d-Penicillamine in Aqueous Solution

Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)3 and PhSb(SOCPh)2

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Thiobenzoates of lead (II) and bismuth (III). The crystal and molecular structures of (AsPh₄) [Pb(SOCPh)₃] and Pb(SOCPh)₂(S₂CP{c-C₆H₁₁}₃)

Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)₃ and PhSb(SOCPh)₂