Perturbation of Degeneracy of the Cope Rearrangement by the Crystal Lattice of the β-Form of 1,5-Dimethylsemibullvalene-2,6-dicarbonitrile As Studied by Variable-Temperature Solid-State Carbon-13 Spectroscopy and X-ray Crystallography at Cryogenic Temperatures

2000 ◽  
Vol 122 (18) ◽  
pp. 4455-4463 ◽  
Author(s):  
Alan Benesi ◽  
Rüdiger Bertermann ◽  
Hans Förster ◽  
Markus Heubes ◽  
Lloyd M. Jackman ◽  
...  
Keyword(s):  
Solid State ◽  
Crystal Lattice ◽  
Variable Temperature ◽  
Cope Rearrangement ◽  
Cryogenic Temperatures ◽  
X Ray ◽  
X Ray Crystallography

Synthesis, characterization, and reactivity of the first hafnium alkyl complex stabilized by amidate ligands

2005 ◽  
Vol 83 (6-7) ◽  
pp. 1037-1042 ◽  
Author(s):  
Robert K Thomson ◽  
Brian O Patrick ◽  
Laurel L Schafer
Keyword(s):  
Coordination Chemistry ◽  
Solid State ◽  
Key Words ◽  
Low Temperatures ◽  
Variable Temperature ◽  
X Ray ◽  
X Ray Crystallography ◽  
Exchange Processes ◽  
Hydrolysis Of

A photo and thermally stable bis(amidate)–dibenzyl complex of Hf ([DMP(NO)Ph]2Hf(CH2Ph)2(THF) (2a) was formed as a monosolvated THF adduct in near quantitative yield from Hf(CH2Ph)4 and N-2,6-dimethylphenyl(phenyl)amide (1). Isomerization between the THF-bound product and the THF-free product can be observed visually by the conversion from a red-orange product at low temperatures to a pale yellow product at high temperatures. Solid-state crystallographic characterization of the orange product confirmed its constitution as a monosolvated species. Kinetic parameters for the exchange of the THF moiety were determined from variable-temperature NMR experiments. The product of the hydrolysis of the Hf dibenzyl species by water was characterized by X-ray crystallography, and was found to be a rare tetrametallic Hf oxo cluster species (3).Key words: hafnium, protonolysis, amidate, coordination chemistry, organometallic chemistry, exchange processes.

N-Methyldiethanolamine-Modified Titanium Isopropoxide: X-Ray Crystal Structure of [Ti2(μ2-(OCH2CH2)2NCH3)(μ2-OPri)(OPri)5]

2002 ◽  
Vol 55 (8) ◽  
pp. 513 ◽  
Author(s):  
T. Kemmitt ◽  
N. I. Al-Salim ◽  
G. J. Gainsford
Keyword(s):  
Solid State ◽  
Variable Temperature ◽  
Titanium Isopropoxide ◽  
State Structure ◽  
X Ray ◽  
Coordination Numbers ◽  
X Ray Crystallography ◽  
Exchange Processes ◽  
Amine Function ◽  
Ligands Exchange

A highly fluxional dititanium N-methyldiethoxoamine hexaisopropoxide complex was isolated from reactions of N-methyldiethanolamine with Ti(OPri)4. X-ray crystallography identified the solid state compound as the unsymmetrical complex Ti2(μ2-(OCH2CH2)2NCH3)(μ2-OPri)(OPri)5. In solution, the time-averaged structure was shown by NMR to be symmetrical. The amine function coordinates to both titanium atoms alternately, while the isopropoxide ligands exchange to maintain equal coordination numbers on both titaniums. Variable temperature NMR demonstrates that the exchange processes slow on cooling, and a spectrum consistent with the solid-state structure is apparent at –50�C.

A Solid State Study of Keto-enol Tautomerismin Three Naphthaledene Schiff Bases

2012 ◽  
Vol 65 (5) ◽  
pp. 552 ◽  
Author(s):  
Gregory K. Pierens ◽  
T. K. Venkatachalam ◽  
Paul V. Bernhardt ◽  
Mark J. Riley ◽  
David C. Reutens
Keyword(s):  
Solid State ◽  
Absorption Band ◽  
Schiff Bases ◽  
Variable Temperature ◽  
Colour Change ◽  
Uv Spectra ◽  
X Ray ◽  
X Ray Crystallography ◽  
State Study ◽  
Tautomeric Composition

Three naphthaledene Schiff bases were synthesized and a detailed analysis by variable temperature X-ray crystallography and solid state electronic spectra was undertaken to assess the tautomeric composition. The crystal structures showed no significant changes despite the compounds changing colour with temperature. Solid state UV spectra were acquired at low temperature and showed that the major absorption band broadened as the temperature was increased. In one compound absorptions were observed that increased in intensity as the temperature increased. For these compounds, the major contribution to the colour change is the broadening of the absorption band as a function of temperature and not the change in enol-keto tautomeric composition.

scholarly journals A Mixed-metal Mixed-halide Complex Prepared from Zerovalent Copper and Lead Salts: Solution and Solid-state Chemistry

1999 ◽  
Vol 23 (11) ◽  
pp. 670-671
Author(s):  
Larisa A. Kovbasyuk ◽  
Olga Yu. Vassilyeva ◽  
Vladimir N. Kokozay ◽  
Wolfgang Linert ◽  
Paul R. Raithby
Keyword(s):  
Solid State ◽  
Direct Interaction ◽  
Solid State Chemistry ◽  
X Ray ◽  
Mixed Metal ◽  
X Ray Crystallography ◽  
Halide Complex ◽  
Layer Arrangement ◽  
Lead Salts

The mixed-metal mixed-halide complex [CuPbBrlL2]2 has been prepared by the direct interaction of zerovalent copper with lead halides and 2-dimethylaminoethanol (HL) in dmso and has been characterized by X-ray crystallography; the structure shows a layer arrangement of the tetranuclear metal units through the μ3-halogen bridging.

Bis(1-phenyl-1-propyne) complexes of tungsten(II): crystal structures of [WI2(CO)(NCR)(η2-MeC2Ph)2] (R = Me, Et, or Ph)

2001 ◽  
Vol 79 (3) ◽  
pp. 263-271
Author(s):  
Paul K Baker ◽  
Michael GB Drew ◽  
Deborah S Evans
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Crystal Structures ◽  
Octahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Alkyne Complexes ◽  
First Time

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

scholarly journals Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4404
Author(s):  
Shengyang Guan ◽  
David C. Mayer ◽  
Christian Jandl ◽  
Sebastian J. Weishäupl ◽  
Angela Casini ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Density Functional ◽  
Bulk Material ◽  
Variable Temperature ◽  
Active Phase ◽  
Solvent Free ◽  
X Ray Diffraction ◽  
X Ray ◽  
Aurophilic Interactions

A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff
Keyword(s):  
Absorption Spectrum ◽  
Solid State ◽  
Single Crystal ◽  
Structural Characterization ◽  
Heterometallic Complex ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

scholarly journals Simple Methylcadmium Alkoxides

2007 ◽  
Vol 62 (10) ◽  
pp. 1339-1342 ◽  
Author(s):  
Surajit Jana ◽  
Tania Pape ◽  
Norbert W. Mitzel
Keyword(s):  
Mass Spectrometry ◽  
Solid State ◽  
Molecular Formula ◽  
Equimolar Ratio ◽  
X Ray ◽  
X Ray Crystallography ◽  
Elemental Analyses ◽  
Solid State Structures ◽  
Structural Aspects ◽  
C Nmr

The reaction of dimethylcadmium with alcohols R-OH in equimolar ratio leads to the formation of tetrameric methylcadmium alkoxides with molecular formula [(MeCd)4 (OR)4] [R = Me (1), Et (2) and iPr (3)]. These compounds have been characterised by 1H, 13C NMR and IR spectroscopy, by mass spectrometry, elemental analyses and by X-ray crystallography (for 2 and 3). The solid state structures show distorted cubane-type aggregates with Cd4O4 cores. The structural aspects and the spectroscopic characterisations of these compounds are discussed.

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