The preparation of bis(perfluoroethyl) tellurium difluoride and dichloride, trans perfluoroethyl tellurium monochloride tetrafluoride, trans bis(perfluoroethyl) tellurium tetrafluoride; and the preparation and X-ray crystal structure of perfluoroethyl tellurium trifluoride

1985 ◽  
Vol 63 (8) ◽  
pp. 2273-2280 ◽  
Author(s):  
Clement Lau ◽  
Jack Passmore ◽  
E. Keith Richardson ◽  
Tom K. Whidden ◽  
Peter S. White
Keyword(s):  
Vibrational Spectra ◽  
Electron Pair ◽  
Lone Pair ◽  
Axial Position ◽  
X Ray Diffraction ◽  
Tellurium Atom ◽  
Nmr Spectrum ◽  
X Ray ◽  
R Factor ◽  
Trigonal Bipyramidal

The reaction of (C2F5)2Te and XeF2 in a slurry of SO2ClF yielded (C2F5)2TeF2 essentially quantitatively. Chlorine and (C2F5)2Te gave (C2F5)2TeCl2. Both (C2F5)2TeF2 and (C2F5)2TeCl2 were assigned a trigonal bipyramidal geometry, on the basis of their 19F nmr and vibrational spectra, with the lone pair and C2F5 groups in equatorial, and the halogens in the axial positions. Perfluoroethyl tellurium trifluoride was prepared essentially quantitatively by the reaction of C2F5TeTeC2F5 and XeF2 in liquid SO2F2. The generally inert SO2ClF was found to react with C2F5TeTeC2F5 to give C2F5TeClxF3−x, and sulphur dioxide. The structure of C2F5TeF3 was determined by X-ray diffraction. The crystals are tetragonal with a = 10.129(4), c = 25.561(6) Å, and Z = 16. The structure was refined in space group I41/a to a conventional R factor of 0.051 for 901 observed reflections with I ≥ 3σ(I). Each tellurium atom is surrounded by two terminal fluorine atoms and two bridging fluorine atoms and a C2F5 group in an axial position around the apex of a distorted square pyramid. The square-pyramidal units are linked by symmetrical cis bridging atoms into endless chains with bridging angles of 180° and 177°. The geometry of the (C2F5TeF4) group is consistent with steric activity of the non-bonded electron pair. The 19F nmr and Raman spectra of C2F5TeF3 were recorded and the Raman spectrum assigned. Trans-C2F5TeClF4 was prepared by the reaction of C2F5TeTeC2F5, and an excess of ClF. The trans octahedral geometry of C2F5TeClF4 was unambiguously assigned from its 19F nmr and vibrational spectra. A mixture of trans-(C2F5)2TeF4 and trans-C2F5TeClF4 was obtained from the reaction of (C2F5)2Te and an excess of ClF. Trans geometry of (C2F5)2TeF4 was unambiguously assigned from its 19F nmr spectrum.

Structure of russellite (Bi2WO6): origin of ferroelectricity and the effect of the stereoactive lone electron pair on the structure

2018 ◽  
Vol 74 (3) ◽  
pp. 295-303 ◽  
Author(s):  
Hiroki Okudera ◽  
Yuka Sakai ◽  
Kentaro Yamagata ◽  
Hiroaki Takeda
Keyword(s):  
Low Temperature ◽  
Lone Electron Pair ◽  
Electron Pair ◽  
Lone Pair ◽  
Orthorhombic Phase ◽  
Electrostatic Charge ◽  
X Ray Diffraction ◽  
Coordination Environment ◽  
X Ray ◽  
Powder Neutron Diffraction

The structure of the low-temperature polar (orthorhombic) phase of russellite (Bi2WO6) was examined on artificial specimens with precise single-crystal X-ray diffraction experiments. The final atomic arrangement thus obtained was identical to that reported by Knight [Miner. Mag. (1992), 56, 399–409] with powder neutron diffraction. The residual density attributable to a stereochemically-active lone pair of electrons of bismuth was prominent at approximately the centre of a larger cap of BiO8 square antiprisms, that is on the line from the Bi sites to an adjacent WO4 2− slab along the b-axis direction. Quite uneven Bi—O distances and the formation of a vacant coordination hemisphere (within 3 Å) should, therefore, be ascribed to the strong demand of bismuth to form shorter Bi—O bonds to use up its electrostatic charge within its coordination environment. The shift of bismuth along −c propagates via the correlated shift of the W site and these cooperative shifts cause ferroelectricity in the compound. This propagation was easily effected by the intrusion of molecules such as acetone into the structure.

Darstellung, 11B-NMR- und Schwingungsspektren von c/s-Monoethylmononitrotetrahydro- c/050-hexaborat(2-) sowie Kristallstruktur von cis (Ph4As)2[B6H4(C2H5)(NO2)] / Synthesis, 11B NMR and Vibrational Spectra of cis-Monoethylmononitrotetrahydroc-closo-hexaborate(2-) and Crystal Structure of cis-(Ph4As)2[B6 H4 (C2H5 )(NO2)]

1999 ◽  
Vol 54 (6) ◽  
pp. 772-776 ◽  
Author(s):  
C. Drewes ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Diffraction Analysis ◽  
Vibrational Spectra ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Dichloromethane Solution ◽  
Triclinic Space Group ◽  
X Ray ◽  
11B Nmr ◽  
Ir And Raman

By electrochemical oxidation of (n-Bu4N)[B6H5Hfac(C2H5)] in the presence of nitrite ions and of the base DBU in dichloromethane solution cis-[B6H4(C2H5)(NO2)]2- is formed. X-ray diffraction analysis has been performed on a single crystal of cis-(Ph4 As)2[B6H4(C2H5)(NO2)] (triclinic, space group P1; a = 10.673(4). b = 10.907(4), c = 21.237(4) A, α = 80.789(4), β = 83.117(4), γ = 66.548(2)°, Z = 2). The 11B NMR spectrum is consistent with a disubstituted octahedral B6 cage with local Cs symmetry. The IR and Raman spectra exhibit characteristic CH3, CH2, NO2, BN, BH and B6 vibrations

Hydrido(acylenolato)cobalt(III)-Verbindungen mit Trimethylphosphan- Liganden: Insertionsreaktionen mit Alkinen und die ersten Carbonylcobalt(III)-Komplexe / Hydrido(acylenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands: Insertion Reactions with Alkynes and the First Carbonylcobalt(III) Complexes

2000 ◽  
Vol 55 (8) ◽  
pp. 707-717 ◽  
Author(s):  
Hans-Friedrich Klein ◽  
Xiaoyan Li ◽  
Ulrich Flörke ◽  
Hans-Jürgen Haupt
Keyword(s):  
Axial Position ◽  
Coupling Reactions ◽  
Carbonyl Complexes ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
Insertion Reactions ◽  
X Ray ◽  
Reversible Transformation ◽  
Tert Butyl ◽  
Trigonal Bipyramidal

Abstract Formal insertion of phenylethyne into Co-H functions of mer-octahedral acyl(enolato)-cobalt(III) hydrides 1-3 proceeds under ambient conditions affording η1-vinylcobalt(III) compounds where the dianionic acyl(enolato) ligands are derived from 2-formyl-4-phenyl-cyclohexanone (4), 1-formyl-cyclohexan-2-one (5), and 3-hydroxo-2,3-diphenyl-propenal (6). Dissociation and association of trimethylphosphane results in a reversible transformation of penta-coordinate complexes 4 -6 into hexa-coordinate ones 7 -9, respectively, involving different tautomeric vinyl species. In toluene solution 9 rearranges by reductive C,C coupling into a 5,6-η2-olefin(enolato)cobalt(I) complex 10. Trimethylsilylethyne undergoes a hydrolytic desilylation reaction which is followed by reductive C,C-coupling reactions of acyl and vinyl functions selectively producing chelating η1-enolato-5,6-η2-olefin ligands in cobalt(I) com ­ pounds 13 -16 where the (ax,eq)chelating ligands are derived from 1-formyl-cyclohexan-2-one (13), 3-hydroxo-2,3-diphenyl-propenal (14), 2-formyl-α-tetralone (15), and 2-formyl-4-tert-butyl-cyclohexanone (16). An axial position of the enolato-O donor in the trigonal bipyramidal configuration of complex 15 has been confirmed by X-ray diffraction analysis. With 1,4-bis(trimethylsilyl)buta-diyne 1,2-addition in cobalt(III) hydrides 2, 3, 11 (as deriverd from 2-formyl-α-tetralone), and 12 (as derived from 2-formyl-4-tert-butyl-cyclohexanone) produces 2-metalated vinyl groups in compounds 17 -20. Dissociation of trimethylphosphane from 17 and 19 does not activate C,C coupling at the cobalt(III) centre of penta-coordinate 21 and 22. Steric congestion in compounds 17, 18, and 20 favours exchange of trimethylphosphine for carbon monoxide affording the first octahedral carbonyl complexes of cobalt (d6) (23 -25). In the crystal and in solution a meridional configuration is adopted by complex 23 with the CO group in a position opposite to the acyl function.

Darstellung, 11B-NMR- und Schwingungsspektren von Aminohexahydro-closo-hexaborat(1–), [B6H6(NH2)]- sowie Kristallstruktur von Cs[B6H6(NH2)] · H2O / Preparation, 11B NMR and Vibrational Spectra of Aminohexahydro-closo-hexaborate(1–), [B6H6(NH2)]-, and the Crystal Structure of Cs[B6H6(NH2)] · H2O

1995 ◽  
Vol 50 (1) ◽  
pp. 11-14 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Vibrational Spectra ◽  
Nmr Spectra ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Aqueous Alkaline Solution ◽  
Nmr Spectrum ◽  
X Ray ◽  
11B Nmr ◽  
Ir And Raman

Aminohexahydro-closo-hexaborate(1–), Crystal Structure, 11B NMR Spectra, Vibrational SpectraBy reduction of [B6H5(NO2)]2- with Fe2+ in aqueous alkaline solution [B6H6(NH2)]- is formed. The compound has been separated by extraction with dichloromethane in the presence of tetrabutylammoniumbromid and precipitated from the organic phase by adding CsCH3COO/C2H5OH. The Crystal structure of Cs[B6H6(NH2)] · H2O has been determined by single crystal X-ray diffraction analysis; monoclinic space group C2 with a = 22.1075(14), b = 6.491(2), c = 5.9570(4) A, β = 100.168(6)°. The 11B NMR spectrum is consistent with a mono-hetero-substituted octahedral B6 cage with local C4v symmetry. The IR and Raman spectra exhibit characteristic N–H, B–H and B6 vibrations.

Crystal structure and solution studies of the product of the reaction of β-mercaptoethanol with vanadate

1999 ◽  
Vol 77 (12) ◽  
pp. 2088-2094 ◽  
Author(s):  
Sudeep Bhattacharyya ◽  
Raymond J Batchelor ◽  
Frederick WB Einstein ◽  
Alan S Tracey
Keyword(s):  
Crystal Structure ◽  
Mixed Solvent ◽  
Axial Position ◽  
Acetonitrile Solution ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Solution Studies ◽  
Alkaline Conditions

Reaction of β-mercaptoethanol with vanadate under slightly alkaline conditions provided a crystalline complex that was characterized by X-ray diffraction and FTIR spectroscopy. The complex was dimeric in structure with a central [VO]2 core and a pentacoordinate, crudely trigonal bipyramidal arrangement about each vanadium atom with a sulphur occupying a pseudo-axial position. A single 51V NMR signal was observed for this complex when dissolved in water, chloroform or acetonitrile. A large influence of acetonitrile on the vanadium chemical shift suggested the possibility of reaction with acetonitrile. FTIR showed the presence of two complexes in acetonitrile solution but only one in chloroform or water. Mixed solvent studies were carried out in an effort to further characterize the solution complexes. Crystal structure of [{VO2(OC2H4S)}2][NEt4]2: monoclinic, space group P21/n,. a = 8.3451(17), b = 16.954(4), c = 10. 2064(25) Å; β = 101. 271(18)°; V = 1416.2 Å3; Z = 2; RF = 0.048 for 1355 data (Io 2..5σ (Io) and 147 variables.Key words: mercaptoethanol, vanadate, vanadium NMR, X-ray diffraction, FTIR, thiolate.

Synthesis, Vibrational Spectra, Mass Spectrum and Crystal Structure of Tri-n-butyltin Diphenylphosphinate (n-Bu)3SnO2PPh2

1995 ◽  
Vol 50 (9) ◽  
pp. 1343-1347 ◽  
Author(s):  
Abdel-Fattah Shihada ◽  
Frank Weller
Keyword(s):  
Crystal Structure ◽  
Mass Spectrum ◽  
Diffraction Study ◽  
Raman Spectra ◽  
Vibrational Spectra ◽  
Ir And Raman Spectra ◽  
X Ray Diffraction ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Ir And Raman

AbstractTri-n-butyltin diphenylphosphinate (n-Bu)3SnO2PPh2 has been synthesized by the reaction of (n-Bu3Sn)2O with Ph2POCl in toluene. An X-ray diffraction study of (n-Bu3)SnO2PPh2 shows that the structure is polymeric and consists of helical chains in which (n-Bu)3Sn groups are linked by O-P-O bridges. The geometry about tin is trigonal bipyramidal, with n-butyl groups in equatorial positions and an axial O-Sn-O angle of 176.2 (2)°. IR and Raman spectra of (n-Bu)3SnO2PPh2 are given and assigned. The mass spectrum is reported and discussed.

Darstellung, 11B-, 13C-NMR-und Schwingungsspektren von Aminom ethylhexahydro-closo-hexaborat(1-), [B6H6(CH2NH2)]- sowie Kristallstrukturen von Cs[B6H6(CH2NH2)] und K[B6H6(CH2NH2)] / Preparation, 11B, 13C NMR and Vibrational Spectra of Aminomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2NH2)]-, and Crystal Structures of Cs[B6H6(CH2NH2)] and K[B6H6(CH2NH2)]

1994 ◽  
Vol 49 (9) ◽  
pp. 1267-1271 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
13C Nmr ◽  
Vibrational Spectra ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
X Ray ◽  
C Nmr

By reaction of [B6H6]2- with N-(chloromethyl)phthalimide in dichloromethane the intermediate phthalimidomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2(NC8O2H4)]-, is formed which with an excess of hydrazine reacts to give am inomethylhexahydro-closo-hexaborate(1-). The crystal structures of Cs[Bf,H6(CH2NH2)] and K[B6H6(CH2NH2)] have been determined by single crystal X -ray diffraction analysis. They are monoclinic, space group C2/m with a = 11.123(6), b = 6.8441(11), c = 12.810(7) Å, β = 124.032(5)° for Cs[B6H6(CH2NH2)] and with a = 10.767(2), b = 6.6255(6), c = 12.2648(14) Å, β = 123.880(10")° for K [B6H6(CH2NH2)]. The 11B NMR spectrum is consistent with a monohetero substituted octahedral B6 cage with local C4v symmetry. In the 13C NMR spectrum of Cs[B6H6(CH2NH2)] a quartet at 32.7 ppm with 1J(C,B) 65 Hz is observed. The IR and Ram an spectra exhibit characteristic CH, NH, BH and B6 vibrations

Darstellung, 11B-, 13C-NMR- und Schwingungsspektren von Cs2[B6Cl5(p-C6H4(NI-I2))] sowie Kristallstruktur von (Ph4P)2[B6Cl5(p-C6H4(NH2))]·2CH3CN · 0,5 Et2O / Preparation, 11B, 13C NMR and Vibrational Spectra of Cs2[B6Cl5(p-C6H4(NH2))] and Crystal Structure of (Ph4P)2[B6Cl5(p-C6H4(NH2))]· 2CH3CN · 0.5 Et2O

2001 ◽  
Vol 56 (1) ◽  
pp. 85-89
Author(s):  
S. Zander ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
13C Nmr ◽  
Vibrational Spectra ◽  
Amino Derivative ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Triclinic Space Group ◽  
X Ray

Abstract By reduction of [B6Cl5(p-C6H4 (NO2))]2- with hydrazine in the presence of Raney nickel in dichlorom ethane solution the amino derivative [B6Cl5(p-C6H4(NH2)]2-is formed. X -ray diffraction analysis has been performed on a single crystal of (Ph4P)2[B6Cl5(p-C6H4(NH2] ·2CH3CN-0,5Et2O(triclinic, space group P1̅, a = 12.870(6), b = 12.9406(5), c = 35,870(7) Å , a = 91,63(4), ß = 93,22(7), γ = 98,04(8)°, Z = 2). The 11B NMR spectrum is consistent with a monosubstituted B6 cluster. The IR and R am an spectra exhibit characteristic BB, CH , CC, and NH vibrations, respectively.

scholarly journals Dimethylantimonazid: Synthese, Spektren und Kristallstruktur Dimethylbismutazid: Synthese und Kristallstruktur Trimethylbleiazid: Verfeinerung der Kristallstruktur / Dimethyl Antimony Azide: Preparation, Spectra and Crystal Structure Dimethyl Bismut Azide: Synthesis and Crystal Structure Trimethyl Lead Azide: Refinem ent of the Crystal Structure

1985 ◽  
Vol 40 (10) ◽  
pp. 1320-1326 ◽  
Author(s):  
Joachim Müller ◽  
Ulrich Müller ◽  
Almuth Loss ◽  
Jörg Lorberth ◽  
Harald Donath ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Diffraction Data ◽  
Lone Pair ◽  
Lead Azide ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Synthesis And Crystal Structure ◽  
Space Group ◽  
X Ray ◽  
Trigonal Bipyramidal

Reaction of Me2SbBr or Et2SbBr with AgN3 in ether affords Me2SbN3 and Et:SbN3. respectively. Me2SbN3 can also be obtained from Me2SbNMe2 and HN3 in ether. Me2BiN3 from Me2BiN(SiMe3)3 and HN3 in ether. Me2SbN3 and Et2SbN3 dissolve as monomers in benzene; 1H, 13C, iaN and 15N NMR spectra of the solutions are reported. IR and Raman spectra of solid Me2SbN3 and Et2SbN, as well as the mass spectrum of Me2SbN3 are assigned. The crystal structures of Me2SbN3 and Me2BiN3 were determined by X-ray diffraction data collected at -67 °C (888 and 439 reflexions, R = 0.024 and 0.076. respectively). Both compounds are isotypic, space group Pnma. Z = 4. Crystal data: Me2SbN3, a = 843.6. b = 919.3, c = 744.1 pm: Me2BiN3, a - 870.8. b = 911.3, c = 738.4 pm. In the crystals, the metal atoms are linked via the aN atoms of the azido groups to form endless zig-zag chains. Whereas the Bi -N distances are equal. Sb-N bonds alternate with two different lengths (232 and 243 pm). Including the lone pair of electrons, the metal coordination can be described as distorted trigonal bipyramidal, with nitrogen atoms occupying the apical positions. With new X-ray diffraction data collected at -100 °C, the crystal structure of Me3PbN3 was refined (1692 reflexions, R = 0.036). Crystal data: a = 656.3, c = 1377 pm. space group P3221, Z = 3. It consists of endless metal-nitrogen chains of helical symmetry. the Pb atoms having trigonal bipyramidal coordination.

Elucidation of the structures of the hydridothiolato complexes WH(SC6H2Pri3-2,4,6)3(L)(PMe2Ph), L = PMe2Ph or pyridine, by NMR and X-ray techniques

1995 ◽  
Vol 73 (7) ◽  
pp. 1092-1101 ◽  
Author(s):  
Timothy E. Burrow ◽  
Alan J. Lough ◽  
Robert H. Morris ◽  
Raymond L. Richards
Keyword(s):  
X Ray Diffraction ◽  
Pyridine Ligand ◽  
Nmr Spectrum ◽  
X Ray ◽  
H Nmr ◽  
Pyridine Ligands ◽  
Trigonal Bipyramidal ◽  
Hydride Ligand ◽  
Nmr Methods

Measurement of the T1 values of the 31P nuclei in the unusual capped trigonal bipyramidal complexes WH(tipt)3(PMe2Ph)2 (1, tipt = SC6H2Pri3-2,4,6) and W(2H)(tipt)3(PMe2Ph)2 allows the determination of the phosphorus–hydride distance of 2.2 ± 0.2 Å and the P-W-H angle of about 62 ± 7°. An approximate location of the hydride on an S2P face is proposed on the basis of steric interactions. The crystal structure of WH(tipt)3-(NC5H5)(PMe2Ph) (2) is reported; the WS3NP core consists of a distorted trigonal bipyramidal system with the phosphine and pyridine ligands axial and the thiolate ligands equatorial. The hydride ligand was not located by X-ray diffraction but can be positioned on an open S2P face at an angle P-W-H of about 65°. The small P-W-H angle results in large 2J(H,P) couplings for 1 and 2. The 1H NMR spectrum of complex 2 is assigned by use of NOE and homodecoupling NMR methods. This complex has the same crowded structure in solution as in the crystalline state. The pyridine ligand, which is sandwiched between two tipt aryl groups, is hindered from rotating around the W—N bond. Keywords: molybdenum, tungsten, thiolate, hydride, NMR, NOE.

Sign in / Sign up

Export Citation Format

Share Document