Nukleophile Substitution an Thionyl- und Sulfurylchlorid mit Metallaten. Synthese und Struktur der SO- bzw. S 0 2-Komplexe [(C6H5O)3P]2(CO)2Fe(SOn)(n=1, 2) / Nucleophilic Substitution at Thionyl- and Sulfuryl Chloride by Metallates. Synthesis and Structure of the SO- and SO2-Complexes [(C6H5O)3P]2(CO)2Fe(SOn)(n=1, 2)

1985 ◽  
Vol 40 (10) ◽  
pp. 1383-1389 ◽  
Author(s):  
Ingo-Peter Lorenz ◽  
Wolfgang Hiller ◽  
Michael Conrad
Keyword(s):  
Nucleophilic Substitution ◽  
Structure Analysis ◽  
Sulfur Atom ◽  
Equatorial Plane ◽  
Sulfur Oxide ◽  
Air Oxidation ◽  
X Ray ◽  
Carbonyl Ligands ◽  
Trigonal Bipyramidal ◽  
Equator Plane

The synthesis of the SO- and SO2-complexes 3 and 4 follows equations (1) and (3) by nucleophilic substitution of SOCl2 or SO2Cl2 by the same metallate 2. 4 can also be obtained by simple air oxidation of solutions of 3 according to equation (2). Spectroscopic investigations indicate a trigonal bipyramidal configuration on iron with both phosphite ligands in axial positions and the sulfur oxide ligands in equatorial positions together with both carbonyl ligands. The X-ray structure analysis of the SO2 complex 4 shows the exactly planar coordination of the sulfur atom and the nearly perpendicular orientation of the SO2 plane to the equator plane; thus complex 4 is isolobal to SO3. The SO ligand in 3 coordinates as a 2c-2e-system in a bent structure with both atoms lying in the equatorial plane.

scholarly journals The Chemistry of Heteroarylphosphorus Compounds, Part 16.+ An X-Ray Structural Study of (2-Thienyl)bis(2,2′-biphenylylene)phosphorane. A Comparison with Related Methyl and Aryl bis(2,2′-biphenylylene)- spirophosphoranes

1983 ◽  
Vol 38 (4) ◽  
pp. 465-469 ◽  
Author(s):  
David W. Allen ◽  
Lorraine A. March ◽  
Ian W. Nowell ◽  
John C. Tebby
Keyword(s):  
Least Squares ◽  
Electron Density ◽  
Structural Study ◽  
Equatorial Plane ◽  
Title Compound ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Thienyl Group ◽  
Density Methods ◽  
Least Squares Techniques

AbstractCrystals of the title compound are monoclinic, a= 18.9 93 (11), b = 8.757(5), c= 13.267(8) Å, β = 106.60(5)°, Z = 4 in space group Cc (Cs4 , No. 9). The structure was determined by Patterson and electron-density methods and refined by least squares techniques to R= 0.081, R′ = 0.085 for 1293 independent reflections classified as observed. The molecule is found to adopt an almost regular trigonal bipyramidal geometry in which the two biphenylylene units span apical-equatorial positions and the 2-thienyl group occupies the remaining equatorial site. The 2-thienyl group, which is disordered, does not lie in the equatorial plane, and there is no indication of C2pπ → P3dπ-t interactions between the heteroaryl group and phosphorus. The steric requirements of the 2-thienyl group appear to be comparable with those of methyl and phenyl groups in bis(2,2′-biphenylylene)spiro-phosphoranes.

Die Kristallstruktur von Kalium-bis(hexamethylentetramin)-tris-(isothiocyanato)cuprat(II)-dihydrat, K[Cu(C6H12N4)2(NCS)3] · 2 H2O, einem trigonal-bipyramidalen Kupfer(II) -Komplex / The Crystal Structure of Potassium-bis(hexamethylenetetramine)-tris-(isothiocyanato) cuprate(II )-dihydrate, K[Cu(C6H12N4)2(NCS)3] · 2 H2O, a Trigonal Bipyramidal Cupric Complex

1981 ◽  
Vol 36 (5) ◽  
pp. 649-650 ◽  
Author(s):  
Joachim Pickardt
Keyword(s):  
Crystal Structure ◽  
Aqueous Solution ◽  
Structure Analysis ◽  
Title Compound ◽  
X Ray ◽  
Trigonal Bipyramidal Geometry ◽  
Trigonal Bipyramidal ◽  
Cupric Acetate

From an aqueous solution of cupric acetate containing an excess of KSCN and hexamethy- lenetetramine crystals of the title compound could be obtained. An X-ray structure analysis showed that the cuprate(II) anion has trigonal bipyramidal geometry. The three equatorial positions are occupied by NCS groups, the axial positions by the hexamethylenetetramine molecules

Germanium(II)-Komplexe mit Dithio-at-Chelatliganden / Germanium(II) Complexes with Dithio-ate Chelating Ligands

1990 ◽  
Vol 45 (6) ◽  
pp. 775-780 ◽  
Author(s):  
Hans H. Karsch ◽  
Michael Hollstein ◽  
Gerhard Müller
Keyword(s):  
Structure Analysis ◽  
Germanium Atom ◽  
Chelating Ligands ◽  
X Ray ◽  
Trigonal Bipyramidal

Stable germanium(II)-dithiocarbamate complexes Ge[S2C(NR2)]2 (R = Me, Et) have been obtained from GeCl2 · dioxane and Na[S2C(NR2)]. As an intermediate, Ge(Cl)[S2C(NEt2)] also could be isolated. Likewise, Ge[S2PMe2]2 was synthesized from GeCl2 · dioxane and Na[S2PMe2] and characterized by X-ray structure analysis. The germanium atom acts as a spiro-center for four sulfur atoms in a distorted ψ-trigonal bipyramidal configuration which is established by two anisobidentate dithiophosphinate ligands. The axial Ge—S bonds are significantly longer (mean: 2.722 A) than the equatorial ones (mean: 2.415 A). The variation in the axial bonds is more pronounced (0.058 A) than in the equatorial (0.013 A) Ge—S bonds, but this effect is much smaller than in the comparable Ge[(PMe2)2CPMe2]2 complex.

Halogeno-und Pseudohalogeno-tris(pentahaptocyclopentadienyl)uran(IV)- Komplexe als Lewis-Säuren: Darstellung und Struktur trigonal-bipyramidaler Uran-Organyle des Typs [(η5 -C5H5)3UXL] / Tris(pentahaptocyclopentadienyl)uranium(IV) Halides and Pseudohalides as Lewis-Acids: Preparation and Structure of Uranium Organyls [(η5 -C5H5)3UXL] with Trigonal-Bipyramidal Coordination

1978 ◽  
Vol 33 (12) ◽  
pp. 1393-1397 ◽  
Author(s):  
R. D. Fischer ◽  
E. Klähne ◽  
J. Kopf
Keyword(s):  
Structure Analysis ◽  
Lewis Acids ◽  
Lewis Base ◽  
Lewis Acidity ◽  
X Ray ◽  
Trigonal Bipyramidal Coordination ◽  
Trigonal Bipyramidal ◽  
Linear Alignment ◽  
Specific Reactions

Abstract The first two examples of a novel series of organo-actinide complexes, [Cp3UXL] (Cp = η5 -C5H5, X = halide or pseudohalide anion, L = uncharged Lewis base), are described. The X-ray structure analysis of the system with X = NCS and L = CH3CN confirms an almost linear alignment (H3)CCNUNCS along with the coplanarity of the three Cp ring normals. The remarkable Lewis acidity of certain Cp3UX-compounds appears to be essential for the formation of oligomeric species [Cp3UX]∞ as well as for specific reactions of monomeric CP3UX.

scholarly journals Unexpected fragmentation of bis(triarylstannanethiocarbonyl)disulfides, formation and X-ray structure of triarylstannyl triarylstannanecarbodithioates

2015 ◽  
Vol 3 (1) ◽  
pp. 53-59 ◽  
Author(s):  
Ihor Kulai ◽  
Oleksii Brusylovets ◽  
Nathalie Saffon ◽  
Zoia Voitenko ◽  
Stéphane Mazières ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nucleophilic Substitution ◽  
Sulfur Atom ◽  
Driving Force ◽  
Molecular Iodine ◽  
Membered Ring ◽  
X Ray Diffraction ◽  
X Ray ◽  
Intramolecular Nucleophilic Substitution ◽  
Transition Complex

The synthesis of bis(triarylstannanethiocarbonyl)disulfides was attempted by oxidation of lithium triaryl stannane carbodithioates with molecular iodine. Unexpectedly, the desired compounds are highly unstable and undergo subsequent fragmentation giving triarylstannyl triarylstannanecarbodithioates. The proposed mechanism for this transformation assumes intramolecular nucleophilic substitution with formation of six-membered ring transition complex, stabilized by interaction between tin and thiocarbonyl sulfur atom. Obtained compounds were identified by mass-spectrometry and NMR spectroscopies, and their structures were analyzed by X-ray diffraction. These molecules show the existence of intramolecular non-bonding interactions between the sulfur atoms of the thiocarbonyl moieties and tin atoms. These interactions reflect the tin - sulfur affinity and are the main driving force in the fragmen tation of bis(triphenylstannanethiocarbonyl)disulfides.

Binuclear Fulvalene and Bis(cyclopentadienyl)methane Halfsandwich Complexes of Manganese and Rhenium Containing Tetrahydrothiophene Ligands. X-Ray Structure Analysis of {(CO)2Mn[C5H4-C5H4]Mn(CO)2}(μ-SC4H8)

1993 ◽  
Vol 48 (2) ◽  
pp. 161-170 ◽  
Author(s):  
Max Herberhold ◽  
Martin Biersack ◽  
Thomas E. Bitterwolf ◽  
Arnold L. Rheingold
Keyword(s):  
Molecular Structure ◽  
Ir Spectra ◽  
Structure Analysis ◽  
Nmr Spectra ◽  
X Ray ◽  
Carbonyl Ligands ◽  
Tetrahydrofuran Solution ◽  
C Nmr

AbstractThe photo-induced substitution of carbonyl ligands in the binuclear cyclopentadienyl-type complexes (CO)3M[C5H4(CH2)nC5H4]M(CO)3 (n = 0 (fulvalene), M = Mn (1) and Re (2); n = 1 (bis(cyclopentadienyl)methane), M = Mn (3) and Re (4)) has been studied in the presence of tetrahydrothiophene, SC4H8 (tht). Photodecarbonylation of 1 - 4 in tetrahydrofuran solution leads to solvent-stabilized intermediates which react with tht in the dark to give monosubstituted derivatives (CO)3M[C5H4(CH2)nC5H4]M(CO)2(tht) (1a - 4a). In the case of M = Mn, thtbridged compounds {(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2}(μ-tht) (n = 0 (1b) and n = 1 (3b)) are also obtained which are the exclusive products of the photolysis of 1 and 3 in benzene in the presence of tht. Photodecarbonylation of 1 - 4 in neat tetrahydrothiophene produces disubstituted derivatives in the case of manganese, (tht)(CO)2Mn[C5H4(CH2)nC5H4]Mn(CO)2(tht) (n = 0 (1c) and n = 1 (3c)), whereas only the monosubstituted complexes 2a and 4a could be isolated in the case of rhenium. The molecular structure of the tht-bridged fulvalene complex 1b has been determined by an X-ray structure analysis. A special reaction of dimethyl disulfane with the photolyzed tetrahydrofuran solution of 2 leads to the bis(methylthiolato) compound (CO)3Re[C5H4- C5H4]Re(CO)(SMe)2 (5). The new complexes were characterized by their IR spectra v(CO) and their 1H and 13C NMR spectra.

scholarly journals Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, Crystal Structure, Absolute Configuration and Reactivity

Molecules ◽  
2020 ◽  
Vol 25 (15) ◽  
pp. 3392
Author(s):  
Bogdan Bujnicki ◽  
Jarosław Błaszczyk ◽  
Marek Chmielewski ◽  
Józef Drabowicz
Keyword(s):  
Crystal Structure ◽  
Absolute Configuration ◽  
Sulfur Atom ◽  
Asymmetric Unit ◽  
Orthorhombic System ◽  
X Ray ◽  
X Ray Crystallography ◽  
Trigonal Bipyramidal ◽  
Single Compound ◽  
Leaving Groups

The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P212121, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.

The Ti(IV) Complex of a Benzannulated N-Heterocyclic Carbene

2004 ◽  
Vol 59 (3) ◽  
pp. 348-350 ◽  
Author(s):  
F. Ekkehardt Hahn ◽  
Thorsten von Fehren ◽  
Roland Fröhlich
Keyword(s):  
Structure Analysis ◽  
Mononuclear Complex ◽  
Equatorial Position ◽  
X Ray ◽  
Carbene Complex ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal

The yellow titanium(IV) carbene complex [TiCl4(1)], 2 (1 = N,N’-bis(2,2-dimethylpropyl)benzimidazol-2-ylidene) was synthesized by reaction of TiCl4 and the benzannulated carbene 1 in toluene. The X-ray structure analysis revealed a mononuclear complex with a titanium(IV) center coordinated in a distorted trigonal-bipyramidal fashion by the carbene ligand in an equatorial position and four chloro ligands

scholarly journals Synthesis and crystal structures of two new tin bis(carboranylamidinate) complexes

2017 ◽  
Vol 73 (10) ◽  
pp. 1443-1448 ◽  
Author(s):  
Nicole Harmgarth ◽  
Phil Liebing ◽  
Philipp Hillebrand ◽  
Sabine Busse ◽  
Frank T. Edelmann
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Structure Analysis ◽  
Lone Pair ◽  
Main Reaction ◽  
Similar Reaction ◽  
Main Reaction Product ◽  
X Ray ◽  
Trigonal Bipyramidal Coordination ◽  
Trigonal Bipyramidal

Reaction of 2 equiv. of the lithium carboranylamidinate Li[o-(C2H10B10)C(NCy)(NHCy)] with SnCl2in THF afforded the stannylene compound bis(N,N′-dicyclohexylamidinatocarboranate)tin(II), SnII[o-(C2H10B10)C(NCy)(NHCy)]2(1). A similar reaction of SnCl4with 2 equiv. of Li[o-(C2H10B10)C(NiPr)(NHiPr)] unexpectedly afforded the known solvated pentachloridostannate(IV) salt [Li(THF)4][SnCl5(THF)] as the main reaction product. Small amounts of the new chlorido-tin(IV) bis(carboranylamidinate) bis(N,N′-diisopropylamidinatocarboranate)chloridotin(IV), SnIVCl[o-(C2H10B10)C(NiPr)(NHiPr)][o-(C2H10B10)C(NiPr)2] (2), were isolated as a by-product. Single-crystal X-ray structure analysis revealed aκC,κN-chelating coordination of the carboranylamidinate ligands in both1and2. The Sn atom in1adopts a pseudo-trigonal–bipyramidal coordination under participation of a stereoactive lone pair. In2, a trigonal–bipyramidal coordination of Sn is completed by a chlorido ligand.

An X-ray diffractometer for studying the effect of external fields on the structure and electron distribution of single crystals

1989 ◽  
Vol 22 (1) ◽  
pp. 42-45 ◽  
Author(s):  
L. A. Aslanov ◽  
V. A. Trunov ◽  
G. V. Fetisov ◽  
V. A. Priemyshev ◽  
V. B. Rybakov ◽  
...  
Keyword(s):  
Single Crystals ◽  
Structure Analysis ◽  
Equatorial Plane ◽  
Electron Distribution ◽  
Structural Changes ◽  
Horizontal Axis ◽  
The Other ◽  
External Fields ◽  
X Ray ◽  
Intensity Measurements

A new four-circle X-ray diffractometer (RMD) for single crystals is described that has only one (horizontal) axis of specimen rotation and a movable X-ray tube and detector. The diffractometer is characterized by the equatorial geometry. The equatorial plane rotates about the χ axis lying in this plane whereas the φ axis is fixed. This permits the use of various external (electromagnetic, magnetic etc.) fields applied to specimens along the φ axis. The angles between this direction and all the other crystallographic directions in the specimen remain constant in the course of intensity measurements. The designed RMD diffractometer allows the study of structural changes and electron distribution variations in a crystal subjected to external actions. The geometry and the design of the goniometer are considered in detail. Experiments carried out on the RMD diffractometer have demonstrated its efficiency for precision X-ray structure analysis.

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