Synthesis, spectroscopic and structural studies of O-methyl and O-isopropyl monothiocarbonate (monoxanthate) derivatives of dimethyl-and diphenyltellurium(IV). Crystal structures of Me2Te[SCO2(i-Pr)]2, Ph2Te[SCO2(i-Pr)]2, Me2TeCl[SCO2Me], and Me2TeBr[SCO2(i-Pr)]

1996 ◽  
Vol 74 (11) ◽  
pp. 1968-1982 ◽  
Author(s):  
John E. Drake ◽  
Robert J. Drake ◽  
Layla N. Khasrou ◽  
Anil G. Mislankar ◽  
Raju Ratnani ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Key Words ◽  
Lone Pair ◽  
Supramolecular Interactions ◽  
Equatorial Position ◽  
Structural Studies ◽  
Cell Parameters ◽  
Distorted Trigonal Bipyramid ◽  
Derivatives Of ◽  
Oxygen Atoms

Monothiocarbonate derivatives of diorganotellurium(IV), R2Te[SCO2R′]2, and R2TeX[SCO2R′], where R = Me, Ph; R′ = Me, i-Pr; X = Cl, Br, and I, have been prepared and characterized by vibrational and 1H, 13C, and 125Te NMR spectroscopy. Me2Te[SCO2(i-Pr)]2 (2): P21/n (No. 14) with cell parameters a = 6.942(6) Å, b = 25.599(3) Å, c = 9.404(6) Å, β = 94.48(6)°, V = 1666(1) Å3, Z = 4, R = 0.0648, Rw = 0.0624; Ph2Te[SCO2(i-Pr)]2 (4): P21/n (No. 14) with a = 12.360(4) Å, b = 12.277(3) Å, c = 15.066(3) Å, β = 102.82(2)°, V = 2229.1(9) Å3, Z = 4, R = 0.0368, Rw = 0.0312; Me2TeCl[SCO2Me] (5); P21/c (No. 14) with a = 5.193(2) Å, b = 18.118(4) Å, c = 9.613(5) Å, β = 91.31(6)°, V = 904.2(6) Å3, Z = 4, R = 0.0396, Rw = 0.0361; and Me2TeBr[SCO2(i-Pr)] (8): P21/n (No. 14) with a = 11.701(2) Å, b = 6.250(2) Å, c = 16.152(2) Å, β = 98.43(1)°, V = 1168.4(4) Å3, Z = 4, R = 0.0369, Rw = 0.0325. In all molecules, the immediate environment about tellurium is that of the saw-horse structure in which the lone pair is assumed to be stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. In 2 and 5, the terminal oxygen atoms are oriented toward tellurium, whereas in 4, one O(i-Pr) group is oriented toward tellurium, as it is in 8. In the latter cases, the terminal oxygen atoms act as weak bridges to form a pseudo dimeric species in 4 and a pseudo polymer in 8. Supramolecular interactions in 2 and 5 lead to a sulfur-bridged dimer in the former and a chlorine-bridged polymer in the latter. Key words: structure, tellurium, dimethyl, diphenyl, monothiocarbonates.

Dimethyltellurium(IV) derivatives with mixed 1,1-dithio ligands. Crystal structures of Me2Te[S2CNMe2][S2COEt] and Me2Te[S2CNEt2][S2COMe]

1999 ◽  
Vol 77 (7) ◽  
pp. 1262-1273 ◽  
Author(s):  
John E Drake ◽  
Layla N Khasrou ◽  
Anil G Mislankar ◽  
Raju Ratnani
Keyword(s):  
Lone Pair ◽  
Mixed Ligand ◽  
Equatorial Position ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
Secondary Interactions ◽  
Infrared And Raman Spectroscopy ◽  
Distorted Trigonal Bipyramid ◽  
Derivatives Of

Mixed ligand derivatives of Me2TeLL'2, where L = N,N-dialkyl dithiocarbamate or O,O-alkylene dithiophosphate and L' = O-alkyl dithiocarbonate, have been synthesized and characterized by elemental analysis, 1H, 13C, 31P, and 125Te NMR spectroscopy and infrared and Raman spectroscopy, and X-ray crystallography. Me2Te[S2CNMe2][S2COEt], 8: P[Formula: see text] (no. 2), with cell parameters a = 10.073(3) Å, b = 10.139(2) Å, c = 9.108(2) Å, α = 92.36(2)°, β = 115.55(2)°, γ = 111.19(2)°, V = 760.7(4) Å3, Z = 2, R = 0.0343, Rw = 0.0296. Me2Te[S2CNEt2][S2COMe], 9: P21/c (no. 14) with cell parameters a = 9.881(4) Å, b = 17.671(3) Å, c = 10.149(4) Å, β = 113.65(3)°, V = 1623.3(10) Å3, Z = 4, R = 0.0567, Rw = 0.0514. The immediate environment about tellurium in both molecules is essentially that of a saw-horse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. The S-Te-S angles in the two molecules are 166.87(6)° and 162.0(1)° for 8 and 9, respectively. In both molecules, the Te—S bonds to the dithiocarbamate groups are slightly shorter than those to dithiocarbonates. The dithiocarbamate groups are oriented to give secondary interactions involving the apparently terminal sulfur atoms resulting in Te—S distances of 3.205(2) and 3.277(4) Å, respectively, in 8 and 9. However, only in 9 is there a similar Te—S distance of 3.346(5) Å involving the S2COMe group because in 8, the OEt group of S2COEt, rather than the terminal S atom, is oriented toward Te. Key words: structure, tellurium, methyl, dithiocarbamates, dithiocarbonates, dithiophosphates.

Tetraorganodichalcogenoimidodiphosphinato derivatives of dimethyltellurium(IV) compounds. Crystal structures of Me2Te[(SPPh2)2N]2, Me2TeCl[(SPPh2)2N], Me2TeI[(SPPh2)2N], and Me2TeCl[(OPPh2)(SPPh2)N]

1999 ◽  
Vol 77 (3) ◽  
pp. 356-366 ◽  
Author(s):  
John E Drake ◽  
Robert J Drake ◽  
Anca Silvestru ◽  
Jincai Yang
Keyword(s):  
Sulfur Atom ◽  
Lone Pair ◽  
Axial Position ◽  
Equatorial Position ◽  
X Ray Diffraction ◽  
Cell Parameters ◽  
Distorted Octahedral ◽  
Multinuclear Nmr Spectroscopy ◽  
Distorted Trigonal Bipyramid ◽  
Derivatives Of

Isolation of Me2Te[(SPPh2)2N]2, Me2Te[(OPPh2)(SPPh2)N]2, and the halo derivatives Me2TeX[(SPPh2)2N] and Me2TeX[(OPPh2)(SPPh2)N], where X = Cl, Br, I, was attempted. Four of these were characterized by single crystal X-ray diffraction, while the formation of the others was confirmed by multinuclear NMR spectroscopy. Me2Te[(SPPh2)2N]2, 1; P21/n (No. 14) with cell parameters a = 14.908(3) Å, b = 11.122(5) Å, c = 30.384(6) Å, β = 92.67(2)°, V = 5032(2) Å3, Z = 4, R = 0.0661, Rw = 0.0696. Me2TeCl[(SPPh2)2N], 2; P[Formula: see text] (No. 2) with cell parameters a = 10.553(2) Å, b = 15.512(2) Å, c = 8.769(3) Å, α = 103.19(2)°, β = 94.27(2)°, γ = 85.76(2)°, V = 1391.3(7) Å3, Z = 2, R = 0.0377, Rw = 0.0328. Me2TeI[(SPPh2)2N], 4; P[Formula: see text] (No. 2) with cell parameters a = 10.954(3) Å, b = 15.580(3) Å, c = 8.751(3) Å, α = 103.49(2)°, β = 93.11(3)°, γ = 87.33(2)°, V = 1449.3(7) Å3, Z = 2, R = 0.0586, Rw = 0.0613. Me2TeCl[(OPPh2)(SPPh2)N], 6; P21/c (No. 14) with cell parameters a = 10.441(9) Å, b = 13.672(10) Å, c = 19.521(9) Å, β = 97.16(6)°, V = 2764(3) Å3, Z = 4, R = 0.0546, Rw = 0.0572. The immediate environment about Te is that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. In 1, 2, and 4, one sulfur atom of (SPPh2)2N occupies an axial position. If the second sulfur atom is included in the coordination sphere, then the environment about Te becomes distorted octahedral, for 1, and square pyramidal, for 2 and 4. By contrast, in Me2TeCl[(OPPh2)(SPPh2)N], 6, the oxygen atom, rather than sulfur, is bound to tellurium in the axial position, with the S atom, at best, having a very weak interaction with Te.Key words: structure, tellurium, methyl, tetraphenyldichalogenoimidodiphosphinates.

Synthesis, spectroscopic characterization, and structural studies of organogermanium tri- and monothiocarbonates. Crystal structures of Me2Ge[S2CSEt]2, Ph3Ge[SCO2Me], Ph3Ge[SCO2(i-Pr)], and Ph2Ge[SCO2Me]2

1998 ◽  
Vol 76 (3) ◽  
pp. 319-334 ◽  
Author(s):  
John E Drake ◽  
Jincai Yang
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Sodium Salt ◽  
Variable Temperature ◽  
Spectroscopic Characterization ◽  
Structural Studies ◽  
Cell Parameters ◽  
Derivatives Of ◽  
C Nmr

Two series of S-alkyl trithiocarbonate derivatives of imethylgermane, Me2Ge[S2CSR]2, and halodiphenylgermane, Ph2GeX[S2CSR], where R = Me, i-Pr, n-Pr, n-Bu and X = Cl, Br, and three series of O-alkyl monothiocarbonate derivatives of triphenylgermane, Ph3Ge[SCO2R], diphenylgermane, Ph2Ge[SCO2R], and trimethylgermane, me3Ge[SCO2R], where R = Me, i-Pr, and n-Pr, have been prepared in 73-92% yields by the reaction of the potassium or sodium salt of the appropriate tri- or monothiocarbonic acid with dichlorodimethyl-, chlorotriphenyl-, dichlorodiphenyl-, and chlorotrimethylgermane. The compounds were principally characterized by infrared, Raman, and 1H and 13C NMR spectroscopy, including some variable temperature studies, as well as by mass spectrometry. Me2Ge[S2CSEt]2, 1: P21/m (No. 11) with cell parameters a = 6.647(4) Å, b = 7.423(2) Å, c = 16.290(4) Å, β = 91.07(3)°, V = 803.6(4) Å3, Z = 2, R = 0.0484,Rw = 0.0485. Ph3Ge[SCO2Me],13: P1bar (No. 2) with cell parameters a = 9.970(4) Å, b = 10.660(3) Å, c = 9.853(2) Å, α = 101.78(2)°, β = 109.98(2)°, γ = 89.76(3)°, V = 961.0(5) Å3, Z = 2, R = 0.0534, Rw = 0.0451. Ph3Ge[SCO2(i-Pr)], 14: P 1bar (No. 2) with cell parameters a = 14.386(7) Å, b = 18.598(6) Å, c = 9.223(3) Å, α = 102.85(3)°, β = 94.58(3)°, γ = 108.13(3)°, V = 2256(1) Å3, Z = 2, R = 0.0545, Rw = 0.0552. Ph2Ge[SCO2Me]2, 16: Cc, (No. 9) with cell parameters a = 11.790(4) Å, b = 13.696(5) Å, c = 23.232(6) Å, β = 92.26(3)°, V = 3748(2) Å3, Z = 8, R = 0.0563, Rw = 0.0512. The immediate environment about Ge is that of tetrahedral but the orientations of the thiocarbonate groups display interesting features.Key words: structure, germanium, phenyl, methyl, thiocarbonates.

(Se,O)-Koordinierte Komplexe niedervalenter Hauptgruppenmetalle: Die Kristallstruktur von Bis(N,N-Diethyl-N′-benzoylselenoureato)blei(II) / (S e,O)-Coordinated Complexes of Subvalent Main Group Metals: The Crystal Structure of Bis(N ,N -diethyl-N′-benzoylselenoureato)lead(II)

1994 ◽  
Vol 49 (12) ◽  
pp. 1615-1619 ◽  
Author(s):  
M. Schuster ◽  
W. Bensch
Keyword(s):  
Crystal Structure ◽  
Lone Pair ◽  
Polar Axis ◽  
Crystal Structure Analysis ◽  
Equatorial Position ◽  
Orthorhombic Space Group ◽  
Cell Parameters ◽  
Main Group Metals ◽  
Single Crystal Structure Analysis ◽  
Neighboring Molecule

Bis(N,N-diethyl-N′-benzoylselenoureato)lead(II) has been prepared and characterized by single-crystal structure analysis. Pb(C12H15N2OSe)2 crystallizes in the non-centrosymmetric orthorhombic space group Iba2. The cell parameters are a = 13.206(3), b = 20.542(4), c = 10.089(2) A and Z = 4. R = 0.025. The direction of the polar axis was determined unambig­ uously. Pb(II) is bidentally coordinated to two N,N-diethyl-N′-benzoylselenourea molecules. The coordination polyhedron is a distorted pseudo-trigonal bi-pyramid with one equatorial position occupied by an electron lone-pair. The Pb-Se and Pb-O bond lengths are 2.876(1) and 2.444(4) Å, respectively. In the crystal lattice, each Pb atom also shows interactions with two Se atoms of a neighboring molecule. The Pb-Se distance of that interaction is 3.643 Å.

Effets des sels de terres rares sur quelques phosphates dérivés des metabolites de la glycolyse

1991 ◽  
Vol 69 (8) ◽  
pp. 1281-1287 ◽  
Author(s):  
Claude Rabiller ◽  
Philippe Eymard ◽  
Mahmoud Mesbahi
Keyword(s):  
Nmr Spectroscopy ◽  
Key Words ◽  
Fermentation Process ◽  
Chemical Shifts ◽  
Deuterium Nmr ◽  
Sugar Fermentation ◽  
Phosphoglyceric Acid ◽  
Spectroscopy Studies ◽  
Sugar Derivatives ◽  
Derivatives Of

Phosphate derivatives of glucose and fructose are well-known intermediates in sugar fermentation. Proton and deuterium NMR spectroscopy studies of the fermentation process provide information about proton (deuteron) transfers that are likely to occur in such biotransformations. In this paper we describe the influence of complexation of those metabolites with praseodymium trichloride and of pH on their proton NMR chemical shifts. We determine the conditions under which all the protons of both the α. and β forms of these cyclic sugars are separated. Glucose-1 phosphate was found to be the most suitable derivative for this type of study. Furthermore, comparing the behaviour of these compounds with 2-phosphoglyceric acid allows us to specify the exact conformation of the latter. Key words: phosphate sugar derivatives, NMR, LIS effects.

Supramolecular interactions through lone pair(lp)–π and hydrogen bonding in cobalt(III) and manganese(II) derivatives of N,N′-dimethylvioluric acid: A combined experimental and theoretical study

2015 ◽  
Vol 435 ◽  
pp. 178-186 ◽  
Author(s):  
Rupak Banik ◽  
Subhadip Roy ◽  
Antonio Bauza ◽  
Antonio Frontera ◽  
Antonio Rodríguez-Diéguez ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Theoretical Study ◽  
Lone Pair ◽  
Supramolecular Interactions ◽  
Derivatives Of

A study of a variety of O,O-alkylene dithiophosphate derivatives of triphenyl-and diphenylgermane. Crystal structures of and

1995 ◽  
Vol 73 (7) ◽  
pp. 915-928 ◽  
Author(s):  
John E. Drake ◽  
Anil G. Mislankar ◽  
Raju Ratnani ◽  
Jincai Yang
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Distorted Tetrahedron ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
Derivatives Of

The O,O-alkylene dithiophosphate derivatives of triphenyl- and diphenylgermane, [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] and [Formula: see text] have been prepared and characterized by infrared, Raman, and 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and, in three cases, X-ray crystallography. [Formula: see text] 1, crystallizes as monoclinic in the space group P21/a (No. 14) with the cell parameters a = 12.868(5) Å, b = 11.354(4) Å, c = 17.207(4) Å, β = 95.42(2)°, V = 2502(1) Å3, Z = 4, R = 0.0640, and Rw = 0.0585. [Formula: see text] 2, crystallizes as orthorhombic in the space group Pbca (No. 61) with the cell parameters a = 23.007(4) Å, b = 16.840(4) Å, c = 12.068(3) Å, V = 4657(3) Å3, Z = 8, R = 0.0502, and Rw = 0.0329. [Formula: see text] 3, crystallizes as monoclinic in the space group C2/c (No. 15) with the cell parameters a = 35.48(2) Å, b = 9.275(5) Å, c = 20.78(1) Å, β = 120.93(3)° V = 5866(5) Å3, Z = 8, R = 0.0674, and Rw = 0.0562. As with their methylgermanium analogues, the environment about germanium is essentially that of a distorted tetrahedron, with the terminal sulfur atoms oriented towards germanium rather than away from it, in contrast with analogous noncyclic dithiophosphatogermanes. The substituents on the atoms in both the five- and six-membered rings maintain their nonequivalence in solution, in contrast with tin analogues. Keywords: structure, germanium, diphenyl, triphenyl, cyclic dithiophosphates

Cationic thiolate and selenolate complexes of platinum(IV)

2002 ◽  
Vol 80 (1) ◽  
pp. 41-45 ◽  
Author(s):  
Michael C Janzen ◽  
Michael C Jennings ◽  
Richard J Puddephatt
Keyword(s):  
Nmr Spectroscopy ◽  
Key Words ◽  
Oxidative Addition ◽  
Competitive Reaction ◽  
Methyl Group ◽  
X Ray ◽  
Group Transfer ◽  
Structure Determinations ◽  
Derivatives Of ◽  
Methyl Group Transfer

The reaction of the adamantanoid compounds [Hg4(EPh)6(L)4][ClO4]2 (E = S or Se, L = PEt3 or PPh3) with [PtMe2(bu2bpy)] (bu2bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) occurs easily to give the first examples of cationic thiolate or selenolate derivatives of platinum(IV), [PtMe2(EPh)L(bu2bpy)][ClO4], and the addition is shown to occur with trans stereochemistry. The new complexes are characterized by NMR spectroscopy and when L = PEt3 by X-ray structure determinations. When L = PPh3, a competitive reaction leads to methyl group transfer from platinum to mercury to give MeHgEPh (E = S or Se).Key words: oxidative-addition, platinum, thiolate, selenolate, mercury.

scholarly journals Crystal structure of Zn2(HTeO3)(AsO4)

2021 ◽  
Vol 77 (5) ◽  
pp. 555-558
Author(s):  
Felix Eder ◽  
Matthias Weil
Keyword(s):  
Hydrothermal Reaction ◽  
Three Dimensional ◽  
Lone Pair ◽  
Site Symmetry ◽  
Hydroxide Group ◽  
Molar Ratios ◽  
Distorted Trigonal Bipyramid ◽  
Stereochemical Activity ◽  
By Products ◽  
Oxygen Atoms

Single crystals of Zn2(HTeO3)(AsO4), dizinc(II) hydroxidodioxidotellurate(IV) oxidoarsenate(V), were obtained as one of the by-products in a hydrothermal reaction between Zn(NO3)2·6H2O, TeO2, H3AsO4 and NH3 in molar ratios of 2:1:2:10 at 483 K for seven days. The asymmetric unit of Zn2(HTeO3)(AsO4) contains one Te (site symmetry m), one As (m), one Zn (1), five O (three m, two 1) and one H (m) site. The ZnII atom exhibits a coordination number of 5 and is coordinated by four oxygen atoms and a hydroxide group, forming a distorted trigonal bipyramid. The hydroxide ion is positioned at a significantly larger distance on one of the axial positions of the bipyramid. The [ZnO4OH] polyhedra are connected to each other by corner-sharing to form ∞ 2[ZnO3/2(OH)1/2O1/1] layers extending parallel to (001). The TeIV atom is coordinated by three oxygen atoms and a hydroxide group in a one-sided manner in the shape of a bisphenoid, revealing stereochemical activity of its 5s 2 electron lone pair. The AsV atom is coordinated by four oxygen atoms to form the tetrahedral oxidoarsenate(V) anion. By corner-sharing, [TeO3OH] and [AsO4] groups link adjacent ∞ 2[ZnO3/2(OH)1/2O1/1] layers along [001] into a three-dimensional framework structure.

scholarly journals Über Verbindungen subvalenter Hauptgruppenmetallkationen mit Dithiolaten, 4. Mitteilung [1] Die Kristallstrukturen der Verbindungen Pb[S(CN)C=C(CN)S] und (AsPh4)2{Pb[S(CN)C=C(CN)S]2} / Compounds of Subvalent Main Group Metal Cations with Dithiolates, Part 4 [1] Crystal Structures of Pb[S(CN)C=C(CN)S] and (AsPh4)2{Pb[S(CN)C=C(CN)S]2}

1989 ◽  
Vol 44 (12) ◽  
pp. 1531-1537 ◽  
Author(s):  
Hans-Ulrich Hummel ◽  
Hermann Meske
Keyword(s):  
Crystal Structures ◽  
Complex Anion ◽  
Lone Pair ◽  
Equatorial Position ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Main Group Metal ◽  
Distorted Trigonal Bipyramid

The crystal structures of Pb[S(CN)C=C(CN)S] and (AsPh4)2{Pb[S(CN)C=C(CN)S]2} have been determined by X-ray diffraction. PbS2C4N2, crystallizes in the non-centrosymmetric space group P21 with a = 7.292(3), b = 7.420(3), c = 5.789(2) Å, β = 95.47(5)° and Ζ = 2. The lead atom is coordinated by three S atoms of dithioligands. The coordination sphere around Pb includes a stereochemically active lone-pair and is described as a distorted tetrahedron. (AsPh4)2[Pb(S2C4N2)2] crystallizes in the triclinic space group P1 with a = 17.205(3), b = 13.342(3), c = 12.059(2) Å, α = 106.15(7), β = 102.92(6), γ = 79.50(3)° and Z = 2. In the complex anion {Pb[S(CN)C=C(CN)S]2}2- the Pb-atom is located at a centre of a distorted trigonal bipyramid with a stereochemically active lone-pair in an equatorial position.

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