Die Reaktion eines gemischten Doppelylids mit Ethylenoxid / Reaction of a Mixed Double Ylide with Ethylene Oxide

1978 ◽  
Vol 33 (5) ◽  
pp. 572-573 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Peter Holl
Keyword(s):  
Ethylene Oxide ◽  
Nmr Spectra ◽  
Trigonal Bipyramidal ◽  
Bipyramidal Structure ◽  
Oxygen Atoms

Abstract Dimethyl-trimethylphosphinimino-methylene-phosphorane, (CH3)3P=N-P(CH3)2 = CH2 was found to react with ethylene oxide to form a 1:1 adduct, that was identified as 2,2-dimethyl-2-trimethylphosphinimino -1,2λ5 -oxaphospholane. According to its 1H, 13C, 31P NMR spectra it is assigned a rigid trigonal bipyramidal structure with nitrogen and oxygen atoms in axial positions.

35Cl NQR Spectra of SnCl4 Complexes with Methylaryl Ethers

1986 ◽  
Vol 41 (1-2) ◽  
pp. 211-214 ◽  
Author(s):  
Igor M. Lazarev ◽  
Gennadii V. Dolgushin ◽  
Valentin P. Feshin ◽  
Michail G. Voronkov
Keyword(s):  
Octahedral Structure ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral ◽  
35Cl Nqr ◽  
Bipyramidal Structure ◽  
35Cl Nqr Spectra ◽  
Oxygen Atoms

SnCl4 Complexes with methylaryl ethers and their 35Cl NQR spectra have been obtained. All these complexes, except SnCl4 · 1,2-(CH3O)2C6H4, have a trigonal-bipyramidal structure. The latter compound has an essentially distorted octahedral structure. One of the ligand oxygen atoms takes part in the formation of the SnCl4 complex with 1,3-, 1,4-(CH3O)2C6H4 and RNO2. These complexes have a trigonal-bipyramidal structure too.

17O and 13C NMR spectra of some geminal diacetates

1988 ◽  
Vol 53 (3) ◽  
pp. 588-592 ◽  
Author(s):  
Antonín Lyčka ◽  
Josef Jirman ◽  
Jaroslav Holeček
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
The Other ◽  
13C Nmr Spectra ◽  
Other Hand ◽  
Carboxylic Esters ◽  
C Nmr ◽  
Oxygen Atoms

The 17O and 13C NMR spectra of eight geminal diacetates RCH(O(CO)CH3)2 derived from simple aldehydes have been measured. In contrast to the dicarboxylates R1R2E(O(CO)R3)2, where E = Si, Ge, or Sn, whose 17O NMR spectra only contain a single signal, and, on the other hand, in accordance with organic carboxylic esters, the 17O NMR spectra of the compound group studied always exhibit two well-resolved signals with the chemical shifts δ(17O) in the regions of 183-219 ppm and 369-381 ppm for the oxygen atoms in the groups C-O and C=O, respectively.

17O, 13C, and 29Si NMR spectra of some acyloxy- and diacetoxysilanes and acetoxygermanes

1986 ◽  
Vol 51 (11) ◽  
pp. 2582-2589 ◽  
Author(s):  
Antonín Lyčka ◽  
Jaroslav Holeček ◽  
Karel Handlíř ◽  
Josef Pola ◽  
Václav Chvalovský
Keyword(s):  
Periodic System ◽  
Time Scale ◽  
Nmr Spectra ◽  
Group Element ◽  
29Si Nmr ◽  
Carboxyl Group ◽  
29Si Nmr Spectra ◽  
Oxygen Atoms

The 17O, 13C, and 29Si NMR spectra of (CH3)3SiOC(O)R, CH3(XCH2)Si(OC(O)CH3)2, and R3GeOC(O)CH3 compounds are reported. In the 17O NMR spectra at 350 K the only signal is observed with the two latter series, but two well-resolved signals are displayed with the (CH3)3SiOC(O)R compounds. The equivalence of both oxygen atoms in carboxyl group on the NMR time scale is discussed from the viewpoint of a possible coordination of the oxygen atoms to the IVB group element of the periodic system.

119Sn, 13C and 1H NMR Spectra of Tris(1-butyl)stannyl D-Glucuronate

1997 ◽  
Vol 62 (8) ◽  
pp. 1169-1176 ◽  
Author(s):  
Antonín Lyčka ◽  
Jaroslav Holeček ◽  
David Micák
Keyword(s):  
Chemical Shift ◽  
Carbonyl Group ◽  
1H Nmr ◽  
Equatorial Plane ◽  
Title Compound ◽  
Nmr Spectra ◽  
Hydroxyl Groups ◽  
Carboxylic Group ◽  
H Nmr ◽  
Oxygen Atoms

The 119Sn, 13C and 1H NMR spectra of tris(1-butyl)stannyl D-glucuronate have been measured in hexadeuteriodimethyl sulfoxide, tetradeuteriomethanol and deuteriochloroform. The chemical shift values have been assigned unambiguously with the help of H,H-COSY, TOCSY, H,C-COSY and 1H-13C HMQC-RELAY. From the analysis of parameters of 119Sn, 13C and 1H NMR spectra of the title compound and their comparison with the corresponding spectra of tris(1-butyl)stannyl acetate and other carboxylates it follows that in solutions of non-coordinating solvents (deuteriochloroform) the title compound is present in the form of more or less isolated individual molecules with pseudotetrahedral environment around the central tin atom and with monodentately bound carboxylic group. The interaction of tin atom with oxygen atoms of carbonyl group and hydroxyl groups of the saccharide residue - if they are present at all - are very weak. In solutions in coordinating solvents (hexadeuteriodimethyl sulfoxide or tetradeuteriomethanol), the title compound forms complexes with one molecule of the solvent. Particles of these complexes have a shape of trigonal bipyramid with the 1-butyl substituents in equatorial plane and the oxygen atoms of monodentate carboxylic group and coordinating solvent in axial positions.

IR and 13C, 17O, and 119Sn NMR spectra of some bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids

1991 ◽  
Vol 56 (9) ◽  
pp. 1908-1915 ◽  
Author(s):  
Jaroslav Holeček ◽  
Antonín Lyčka ◽  
Milan Nádvorník ◽  
Karel Handlíř
Keyword(s):  
Infrared Spectroscopy ◽  
Nmr Spectroscopy ◽  
Dicarboxylic Acid ◽  
Nmr Spectra ◽  
Dicarboxylic Acids ◽  
119Sn Nmr ◽  
Carboxylic Groups ◽  
Cyclic Oligomers ◽  
The Media ◽  
Oxygen Atoms

Infrared spectroscopy and multinuclear (13C, 17O, and 119Sn NMR spectroscopy have been used to study the structure of bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids (1-C4H9)2. Sn(X(COO)2), where X = (CH2)n (n = 0-8), CH=CH (cis and trans) and C6H4 (ortho and para).The crystalline compounds are formed by linear or cyclic oligomers or polymers whose basic building units represent a grouping composed of the central tin atom substituted by two 1-butyl groups and coordinated with both oxygen atoms of two anisobidentate carboxylic groups derived from different molecules of a dicarboxylic acid. The environment of the tin atom has a shape of a trapezoidal bipyramid. When dissolvet in non-coordinating solvents, the compounds retain the oligomeric character with unchanged structure of environment of the central tin atom. In the media of coordinating solvents the bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids form complexes whose central hexacoordinated tin atom binds two molecules of the solvent trough their donor atoms. Carboxylic groups form monodenate linkages in these complexes.

scholarly journals The maximum surface area polyhedron with five vertices inscribed in the sphere {\bb S}^{2}

2021 ◽  
Vol 77 (1) ◽  
pp. 67-74
Author(s):  
Jessica Donahue ◽  
Steven Hoehner ◽  
Ben Li
Keyword(s):  
Convex Hull ◽  
Surface Area ◽  
Coordination Polyhedron ◽  
Unit Sphere ◽  
The Other ◽  
Optimal Placement ◽  
The North ◽  
Trigonal Bipyramidal ◽  
Bipyramidal Structure ◽  
North And South

This article focuses on the problem of analytically determining the optimal placement of five points on the unit sphere {\bb S}^{2} so that the surface area of the convex hull of the points is maximized. It is shown that the optimal polyhedron has a trigonal bipyramidal structure with two vertices placed at the north and south poles and the other three vertices forming an equilateral triangle inscribed in the equator. This result confirms a conjecture of Akkiraju, who conducted a numerical search for the maximizer. As an application to crystallography, the surface area discrepancy is considered as a measure of distortion between an observed coordination polyhedron and an ideal one. The main result yields a formula for the surface area discrepancy of any coordination polyhedron with five vertices.

Das 7,8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ5-phosphaspiro[4.4]nonanyl-Kation: Röntgenstrukturanalyse und temperaturabhängige 1H-NMR-Spektren: The 7, 8-Benzo-5-chloro-1,4,4-trimethyl-1-aza-4-azonia-6,9-dioxa-5 λ).5-phosphaspiro[4.4]nonanyl Cation: X-Ray Crystal Structure Determination and Variable 1H NMR Spectra

1992 ◽  
Vol 47 (6) ◽  
pp. 755-759 ◽  
Author(s):  
Thomas Kaukorat ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
1H Nmr ◽  
Nmr Spectra ◽  
Crystal Structure Analysis ◽  
Acceptor Interaction ◽  
Nmr Spectrum ◽  
X Ray ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Donor Acceptor

The 1H NMR spectrum of the spirophosphorane 3 at room temperature indicates dynamic behaviour of the cation. The low-temperature 1H NMR spectra of 3 exhibit two sets of doublets for the protons of the diastereotopic N(CH3)2 groups. The free enthalpy of activation for the dynamic process was determined (58.6 KJ/mole). In the reaction of 3 with sodium tetraphenylborate the crystalline compound, 4, involving the non-coordinating anion, [B(C6H5)4]-, was obtained. The X-ray crystal structure analysis of 4 reveals the presence of a five-membered ring, formally as a result of intramolecular donor-acceptor interaction between the nitrogen atom of the N(CH3)2 group and phosphorus. The geometry at phosphorus deviates somewhat from ideal trigonal bipyramidal.

η3-Allylmeta]l-Schwefel-Komplexe, VI. Anionische η3-Allylnickel- und -palladium-Schwefel-Cluster/ η3-Allylmetal-Sulfur-Complexes, VI. Anionic η3-Allylnickel- and -palladium-Sulfur-Clusters

1983 ◽  
Vol 38 (5) ◽  
pp. 604-610 ◽  
Author(s):  
Reinhard Benn ◽  
Borislav Bogdanović ◽  
Peter Göttsch ◽  
Martin Rubach
Keyword(s):  
Crystal Structure ◽  
Nmr Spectra ◽  
Ionic Structure ◽  
Butyl Lithium ◽  
Sulfur Cluster ◽  
Anionic Clusters ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Lithium Sulfide

Abstractη3-Allylhydrogensulfidonickel (2) reacts with n-butyllithium with elimination of lithium sulfide and formation of the ionic η3-allylnickel-sulfur-cluster [(η3-C3H5Ni)3S2]+[Li(THF)2]- (4). The crystal structure of the analogous THF-TMEDA-adduct (4′) indicates that the nickel and sulfur atoms of the anion adopt a trigonal bipyramidal arrangement, in which the sulfur atoms are at the apices of the bipyramid. The Li(THF)2+ cation in 4 can be replaced by the (n-C4H9)4N+ cation (5). The 1H NMR spectra suggest the presence of two stereoisomers of the anionic clusters in 4 and 5 having C3h and Cs symmetry. In the reaction of η3-allyl- or η3-methallylhydrogensulfidopalladium (6, 6 a) with n-butyl-lithium crystalline compounds having the composition RC3H4PdSLi(THF)≈4, R = H, CH3 (7, 7 a) are obtained; their 1H NMR spectra also reveal the existence of the two stereoisomers having C3h and Cs symmetry. The same type of stereoisomerism is observed with the crystalline [(n-C4H9)4N]+[(η3-C3H5Pd)3S2]- (8) obtained from 7 and (n-C4H9)4N+ClO4-. For 7 and 7 a an ionic structure consisting of trigonal bipyramidal (η3-RC3H4Pd)3S2- anions and Li3S(THF)4+ cations is proposed.

Zum ambidenten Charakter des Cyanotrihydroborat-Liganden in Uran(IV)-Organylen / On the Ambident Nature of the Cyanotrihydroborate Ligand in Organouranium(IV) Complexes

1983 ◽  
Vol 38 (11) ◽  
pp. 1369-1374 ◽  
Author(s):  
R. Dieter Fischer ◽  
Kenan Yünlü
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Colour Change ◽  
Metal Coordination ◽  
Temperature Dependent ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Oligomeric Complex

Both the acceptedly oligomeric complex [(C5H5)3U(μ-NCBH3)]n (1) and its hitherto unknown, appreciably more soluble and volatile homologue, [(CH3C5H4)3U(μ-NCBH3)]n (2), display NIR/VIS spectra typical of trigonal bipyramidal (tbp) metal coordination in the solid state, but of pseudotetrahedral (ψ-Td) coordination e.g. in CH2CI2 and C6H5CH3 solution. The 1H NMR spectra of 2 in these non coordinating solvents can be best explained in terms of temperature dependent equilibria involving the two rapidly interconverting ψ-Td-isomers (CH3C5H4)3U(η3-H3BCN) and (CH3C5H4)3UNCBH3. A reversible colour change: green ⇋ brown at 130-150 °C also suggests the facile rupture of U-H and U-N bonds, respectively, in thermally excited, polycrystalline (2).

The synthesis, Mössbauer and vibrational spectra of some triorganotin derivatives of phosphorus oxyacids

1976 ◽  
Vol 54 (14) ◽  
pp. 2184-2192 ◽  
Author(s):  
T. Chivers ◽  
J. H. G. Van Roode ◽  
J. N. Ruddick ◽  
J. R. Sams
Keyword(s):  
Oxygen Atom ◽  
Sodium Salt ◽  
Vibrational Spectra ◽  
Formula Unit ◽  
Silver Phosphate ◽  
Trigonal Bipyramidal ◽  
Bipyramidal Structure ◽  
Trimethyltin Chloride ◽  
Mössbauer Data ◽  
Derivatives Of

Trimethyltin hypophosphite, Me3SnPO2H2, bis(trimethyltin) phosphite dihydrate, (Me3Sn)2PO3H.2H2O, and bis(triphenyltin) phosphite, (Ph3Sn)2PO3H, have been obtained from the organotin chloride and aqueous solutions of the sodium salt of the corresponding phosphorus oxy-acid. (Me3Sn)2PO3H.2H2O can be dehydrated under vacuum at 25 °C, but disproportionation occurs on heating. Tris(trimethyltin) orthophosphate, (Me3Sn)3PO4, was prepared from trimethyltin chloride and silver phosphate in methanol and gave an adduct formulated as [Formula: see text] after recrystallization from 1,4-dioxane. Vibrational spectra and Mössbauer data for Me3SnPO2H2 are consistent with a trigonal bipyramidal structure in which planar Me3Sn groups are bridged symmetrically by PO2H2 groups. The Mössbauer spectra of (Me3Sn)2PO3H, (Ph3Sn)2PO3H, and (Me3Sn)2PO3H.2H2O suggest that the two tin atoms are in similar (probably pentacoordinate) environments, implying at least one three coordinate oxygen per formula unit. For (Me3Sn)3PO4, the vibrational spectra, Mössbauer data, and physical properties are consistent with a weakly associated structure in which all three tin atoms are in similar environments. It is suggested that association is achieved via the phosphoryl (P=O) oxygen atom, which is weakly coordinated to three tin atoms leading to a distortion of the tetrahedral arrangement around tin towards trigonal bipyramidal.

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