Ringkontraktion am Cyclotrisilazan -System - Synthese und Molekülstrukturen zweifach silylverknüpfter Cyclodisilazane / Ring Contraction in the Cyclotrisilazane System - Synthesis and Molecular Structures of Silyl-Bridged Cyclodisilazanes

1980 ◽  
Vol 35 (11) ◽  
pp. 1359-1365 ◽  
Author(s):  
William Clegg ◽  
Michael Hesse ◽  
Uwe Klingebiel ◽  
George M. Sheldrick ◽  
Lutz Skoda
Keyword(s):  
Crystal Structure ◽  
Molecular Structures ◽  
Lithium Salts ◽  
Ring Contraction ◽  
System Synthesis ◽  
Structure Determinations

Abstract l-(Fluorodiorganylsilyl)-2,2,4,4,6,6-hexamethyl-3-(trimethylsilyl)cyclotrisilazanes react with butyllithium to give the corresponding lithium salts. Ring contraction of the lithium salts with formation of lithiated (fluorodiorganylsilyl)amino-substituted four-membered rings is observed in THF solution. The dimerisation of these cyclodisilazanes with elimination of LiF is demonstrated by crystal structure determinations of three products. Monoclinic and triclinic crystalline modifications of one compound could be isolated.

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

1998 ◽  
Vol 53 (12) ◽  
pp. 1475-1482 ◽  
Author(s):  
Prit Singh ◽  
Sudha Singh ◽  
Vishnu D. Gupta ◽  
Heinrich Nöth
Keyword(s):  
Crystal Structure ◽  
Molecular Structures ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Covalently Bonded ◽  
Bismuth Complex ◽  
Group 15 ◽  
Structure Determinations ◽  
Trigonal Pyramid ◽  
Trigonal Prisms

Abstract Tris-thiobenzoates, Arsenic, Antimony, Bismuth Tris-thiobenzoates of 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

scholarly journals Molecular structures of the pentaphenylcyclopentadienyl iron complexes [(C5Ph5)Fe(CO)2 R] (R = Me, Ph, iPr and Bu)

2021 ◽  
Vol 77 (7) ◽  
Author(s):  
Karlheinz Sünkel ◽  
Christian Klein-Hessling
Keyword(s):  
Crystal Structure ◽  
Iron Complexes ◽  
Molecular Structures ◽  
Electronic Effects ◽  
Alkyl Aryl ◽  
Butyl Lithium ◽  
Catalysed Reaction ◽  
Structure Determinations ◽  
Aryl Complexes ◽  
Phenyl Rings

The PdII-catalysed reaction of [(C5Ph5)Fe(CO)2Br] with Grignard compounds RMgX or butyl lithium gave the iron alkyl/aryl complexes [(C5Ph5)Fe(CO)2 R] (R = Me, Ph, iPr and Bu) in 59–73% yield, namely, dicarbonylmethyl(η5-pentaphenylcyclopentadienyl)iron, [Fe(CH3)(C35H25)(CO)2], dicarbonyl(η5-pentaphenylcyclopentadienyl)phenyliron, [Fe(C6H5)(C35H25)(CO)2], dicarbonyl(isopropyl)(η5-pentaphenylcyclopentadienyl)iron, [Fe(C3H7)(C35H25)(CO)2], and butyldicarbonyl(η5-pentaphenylcyclopentadienyl)iron, [Fe(C4H9)(C35H25)(CO)2]. The crystal structure determinations showed the usual `paddle-wheel' orientation of the phenyl rings, with an average canting angle of ca 50°. The bond parameters are mainly dictated by the steric requirements of the alkyl/aryl groups and only the phenyl complex shows electronic effects.

scholarly journals Crystal and molecular structures of some phosphane-substituted cymantrenes [(C5H4 X)Mn(CO)LL′] (X = H or Cl, L = CO, L′ = PPh3 or PCy3, and LL' = Ph2PCH2CH2PPh2)

2021 ◽  
Vol 77 (10) ◽  
Author(s):  
Karlheinz Sünkel ◽  
Christian Klein-Hessling
Keyword(s):  
Crystal Structure ◽  
Uv Irradiation ◽  
Molecular Structures ◽  
Bond Lengths ◽  
Crystal And Molecular Structures ◽  
Chlorine Substitution ◽  
Small Influence ◽  
Intermolecular Association ◽  
Structure Determinations

UV irradiation of tetrahydrofuran solutions of [CpMn(CO)3] (Cp = π-C5H5 or π-C5H4Cl) in the presence of the phosphanes PPh3 or PCy3 (Cy = cyclohexyl) and Ph2PCH2CH2PPh2 yields the substitution products [CpMn(CO)2PR 3] (R = Ph or Cy) and [CpMn(CO)(Ph2PCH2CH2PPh2)], namely, dicarbonyl(η5-cyclopentadienyl)(triphenylphosphane-κP)manganese(I), [Mn(C5H5)(C18H15P)(CO)2], 1a, dicarbonyl(η5-1-chlorocyclopentadienyl)(triphenylphosphane-κP)manganese(I), [Mn(C5H4Cl)(C18H15P)(CO)2], 1b, dicarbonyl(η5-cyclopentadienyl)(tricyclohexylphosphane-κP)manganese(I), [Mn(C5H5)(C18H33P)(CO)2], 2a, dicarbonyl(η5-1-chlorocyclopentadienyl)(tricyclohexylphosphane-κP)manganese(I), [Mn(C5H4Cl)(C18H33P)(CO)2], 2b, carbonyl(η5-cyclopentadienyl)[1,2-bis(diphenylphosphanyl)ethane-κ2 P,P′]manganese(I), [Mn(C5H5)(C26H24P2)(CO)], 3a, and carbonyl(η5-1-chlorocyclopentadienyl)[1,2-bis(diphenylphosphanyl)ethane-κ2 P,P′]manganese(I), [Mn(C5H4Cl)(C26H24P2)(CO)], 3b, The crystal structure determinations show a very small influence of the chlorine substitution and a moderate influence of the phosphane substitution on the bond lengths. The PR 3 groups avoid being eclipsed with the C—Cl bonds. All the compounds employ weak C—H...O interactions for intermolecular association, which are enhanced by C—H...Cl contacts in the chlorinated products.

Indium Triiodide Complexes of Bis(diphenyIphosphino)ethane (dppe) and its Disulfide (dppeS2)

1999 ◽  
Vol 54 (1) ◽  
pp. 21-25 ◽  
Author(s):  
Marcus Sigl ◽  
Annette Schier ◽  
Hubert Schmidbaur
Keyword(s):  
Crystal Structure ◽  
Ionic Species ◽  
Molecular Structures ◽  
Trans Conformation ◽  
Structure Determinations ◽  
Terminal Complexes ◽  
High Yields

Bis(diphenylphosphino)ethane (dppe) and its disulfide (dppeS2) react with two equivalents of indium triiodide to give high yields of the corresponding 1:2 adducts. According to crystal structure determinations, both compounds are molecular bis-terminal complexes with the ligands in an all-trans conformation. Contrary to previous findings for complexes of the indium trihalides and of GaBr3 and Gal3 with ditertiary phosphines in fixed cis-structure [bis(diphenylphosphino)ethene or -benzene], no iodide redistribution is observed to give the ionic species [(dppe)Inl2]+ [InI4 ]- . The molecular structures are also retained in solution.

1.3-Silylgruppenwanderung im Si2NSiN-Gerüst - Synthese und Molekülstruktur von 1.3-Diaza-2.4-disilacyclobutanen / 1,3-Migration of Silylgroups in the Si2NSiN-System - Synthesis and Molecular Structure of 1,3-Diaza-2,4-disilacyclobutanes

1980 ◽  
Vol 35 (3) ◽  
pp. 275-281 ◽  
Author(s):  
William Clegg ◽  
Uwe Klingebiel ◽  
Cornelia Krampe ◽  
George M. Sheldrick
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Nitrogen Atom ◽  
Structure Determination ◽  
Crystal Structure Determination ◽  
Lithium Salts ◽  
Trimethylsilyl Group ◽  
System Synthesis ◽  
Butyl Lithium

Abstract N-Organylamino-N′,N′-bis(trimethyl)amino-fluoroorganylsilanes react with butyl-lithium to give the corresponding lithium salts. Further reaction of these lithium salts with fluorosilanes leads to the formation of the expected substituted compounds. Diaza-disilacyclobutanes are formed by thermal LiF elimination in THF. The simultaneous 1,3-migration of a trimethylsilyl group from one nitrogen atom to another is demonstrated by the crystal structure determination of the products of two such reactions, with different substituent groups.

Synthese und Kristallstrukturen der Wolfram(VI)-Alkinkomplexe [WCl4(Ph - C≡C - I)(THF)] und [WCl4(Ph-C≡C-Te-C4H9)(THF)] / Synthesis and Crystal Structures of the Tungsten(VI) Alkyne Complexes [WCl4(Ph-C≡C-I)(THF)] and [WCl4(Ph-C≡C-Te-C4H9)(THF)]

1993 ◽  
Vol 48 (8) ◽  
pp. 1105-1111 ◽  
Author(s):  
Michael Plate ◽  
Peter Hofacker ◽  
Werner Massa ◽  
Birgit Schwarz ◽  
Bernhard Neumüller ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Ir Spectroscopy ◽  
Oxygen Atom ◽  
Crystal Structures ◽  
Molecular Structures ◽  
Trans Position ◽  
Space Group ◽  
Structure Determinations ◽  
In Trans ◽  
Alkyne Complexes

[WCl4(Ph-C≡C-I)(THF)] has been prepared by the reaction of trans-[WCl4(SEt2)2] with Ph - C≡C - I in THF solution, whereas [WCl4(Ph-C≡C-Te-nC4H9)(THF)] has been synthesized by the reaction of Ph-C≡C-Te-nC4H9 with tungsten hexacloride in the presence of C2Cl4 and THF. Both complexes were characterized by IR spectroscopy and by crystal structure determinations.[WCl4(Ph-C≡C-I)(THF)]: Space group P21/c, Z = 4, 2617 observed unique reflections, R = 0.064. Lattice dimensions at –70°C: a = 1518.2(3), b = 714.5(1), c = 1540.0(3) pm, β = 90.09(3)°.[WCl4(Ph-C≡C-Te–nC4H9)(THF)]. Space group P1̄, Z = 2, 3911 observed unique reflections, R = 0.067. Lattice dimensions at 20°C: a = 844.0(3), b = 974.6(4), c = 1002.4(3) pm, α = 76.00(4), β= 105.14(1), γ = 82.03(3)°.Both complexes have molecular structures, in which the tungsten atoms are seven-coordi-nate by four chlorine ligands, by the two alkyne carbon atoms, and in trans position to the latter by the oxygen atom of the THF molecule. The WC bond lengths are 198 and 200(1) in the telluro complex and 206 and 196(1) pm in the iodine derivative.

Beiträge zur Chemie des 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan- 6-on Ringsystems: Röntgenstrukturanalysen an einem Bis(2-chlorethyl)amino- und einem Acetamido-substituierten Derivat / Chemistry of the 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-one Ring System: X-Ray Crystal Structure Analysis of a Bis(2-chloroethyl)amino- and of an Acetamido-Substituted Derivative

1994 ◽  
Vol 49 (7) ◽  
pp. 939-949 ◽  
Author(s):  
Axel Fischer ◽  
Ion Neda ◽  
Thomas Kaukorat ◽  
Ralf Sonnenburg ◽  
Peter G. Jones ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Peroxide ◽  
Elemental Sulfur ◽  
Crystal Structure Analysis ◽  
Ring System ◽  
Molecular Structures ◽  
X Ray ◽  
Spectrometric Data ◽  
Structure Determinations ◽  
Phosphoryl Compound

Abstract The reaction of 4,5-benzo-2-chloro-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 with 1,2-bis- (trimethylsiloxy)ethane led to the bisphosphoryl species 2a and to the isomeric bisphosphite derivative 2b. The reaction of 1 with heptamethyldisilazane furnished the expected diphos­phorus compound 3, with two λ3P(III) atoms linked by a methylamino group. Substitution of the chlorine atom of 1 by the 2-chloroethylamino and bis(2-chloroethyl)amino group led to the oxazaphosphorinanones 4 and 6. By oxidation of 4 with the hydrogen peroxide/urea 1:1-adduct, the phosphoryl compound 5 was formed. Oxidation of 4,5-benzo-2-diethyl- amino-3-methyl-1,3,2-oxazaphosphorinan-6-one 7 [1] with hydrogen peroxide, sulfur and se­lenium led to the corresponding phosphoryl, thiophosphoryl and selenophosphoryl com­pounds 8-10. Analogously, the reaction of the dimethylamino- and acetamido-substituted derivatives 11 and 13 [1] with elemental sulfur furnished the thiophosphoryl compounds 12 and 14. X-ray crystal structure determinations of 4 and 14 confirmed the molecular structures, proposed in accord with NMR spectroscopic and mass spectrometric data. The heterocyclic rings are essentially planar. In 14 a hydrogen bond N-H···O (amide) is observed.

Single-crystal X-ray structure determinations of vardenafil, vardenafil dihydrate, vardenafil monohydrochloride trihydrate and vardenafil dihydrochloride hexahydrate

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Dedong Wu ◽  
Faraj Atassi
Keyword(s):  
Crystal Structure ◽  
Synchrotron Radiation ◽  
Single Crystal ◽  
Molecular Structures ◽  
Free Base ◽  
X Ray Diffraction ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Structure Determinations ◽  
Good Agreement

AbstractThe crystal and molecular structures of vardenafil (free, unprotonated base), vardenafil dihydrate and the hydrochloride salts, vardenafil monohydrochloride trihydrate and vardenafil dihydrochloride hexahydrate, were determined by single-crystal X-ray diffraction. The crystal structure of vardenafil monohydrochloride trihydrate is in good agreement with the published crystal structure obtained by powder diffraction using synchrotron radiation. This work shows that the crystal structure of anhydrous vardenafil free base is very similar to the crystal structure of sildenafil free base.

Crystal structure determination of the conformation of two bicyclo[3.3.1]nonan-ones

1985 ◽  
Vol 63 (6) ◽  
pp. 1166-1169 ◽  
Author(s):  
John F. Richardson ◽  
Ted S. Sorensen
Keyword(s):  
Crystal Structure ◽  
Direct Methods ◽  
Chair Conformation ◽  
Molecular Structures ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Final Agreement

The molecular structures of exo-7-methylbicyclo[3.3.1]nonan-3-one, 3, and the endo-7-methyl isomer, 4, have been determined using X-ray-diffraction techniques. Compound 3 crystallizes in the space group [Formula: see text] with a = 15.115(1), c = 7.677(2) Å, and Z = 8 while 4 crystallizes in the space group P21 with a = 6.446(1), b = 7.831(1), c = 8.414(2) Å, β = 94.42(2)°, and Z = 2. The structures were solved by direct methods and refined to final agreement factors of R = 0.041 and R = 0.034 for 3 and 4 respectively. Compound 3 exists in a chair–chair conformation and there is no significant flattening of the chair rings. However, in 4, the non-ketone ring is forced into a boat conformation. These results are significant in interpreting what conformations may be present in the related sp2-hybridized carbocations.

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