Fused Supracyclopentadienyl Ligand Precursors. Synthesis, Structure, and Some Reactions of 1,3-Diphenylcyclopenta[l]phenanthrene-2-one, 1,2,3-Triphenylcyclopenta[l]phenanthrene-2-ol, 1-Chloro-1,2,3-triphenylcyclopenta[l]phenanthrene, 1-Bromo-1,2,3-triphenylcyclopenta[l]phenanthrene, and 1,2,3-Triphenyl-1H-cyclopenta[l]phenanthrene

2006 ◽  
Vol 59 (2) ◽  
pp. 135 ◽  
Author(s):  
Glen D. Dennis ◽  
David Edwards-Davis ◽  
Leslie D. Field ◽  
Anthony F. Masters ◽  
Thomas Maschmeyer ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Good Yield ◽  
Photochemical Reaction ◽  
Subsequent Reaction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Independent Synthesis ◽  
Ligand Precursors

The photochemical reaction of 1,3-diphenylcyclopenta[l]phenanthrene-2-one 5 (phencyclone) with oxygen in acetone leads to the formation of 1,2,3-trihydro-1,2,3-triphenylcyclo-penta[l]phenanthrene 7 (9,10-dibenzoylphenanthrene) along with a trace of the lactone 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8. An independent synthesis of 8 was achieved by the reaction of 5 with FeCl3 in CHCl3. The treatment of 5 with phenyllithium yields 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH in good yield. Subsequent reaction of 9-OH with SOCl2 or SOBr2 in pyridine leads to the formation of the halo-analogues 1-chloro-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Cl and 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br, respectively. Treatment of 9-OH with HBr in acetic acid affords the rearranged product 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one 10 with a trace of 9-Br. Treatment of 9-Cl or 9-Br with zinc in acetic acid affords 1,2,3-tri-phenyl-1H-cyclopenta[l]phenanthrene 9-H. 9,10-Phenanthrenediylbis(phenyl)methanone 7 is formed in good yield upon treatment of 9-OH with HI in acetic acid followed by heating with H2PO4. Compounds 7, 8, 9-Cl, 9-Br, and 10 have been structurally characterized using X-ray crystallography.

Systhesis, Characterization and Spectroscopic Properties of (2E,6E)-2,6-Bis(2,3,4-tri-methoxy-benzylidene)cyclohexanone

2011 ◽  
Vol 396-398 ◽  
pp. 2338-2341
Author(s):  
Xing Chuan Wei ◽  
Zhi Li Liu ◽  
Kun Zhang ◽  
Zhi Yun Du ◽  
Xi Zheng
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Spectroscopic Properties ◽  
Spectral Studies ◽  
Double Bonds ◽  
X Ray ◽  
Π Interactions ◽  
X Ray Crystallography

In this paper, (2E,6E)-2,6-Bis(2,3,4-tri-methoxy -benzylidene)cyclohexanone (omitted as tmbcho) (1) was obtained by the reaction of acetic acid, tetrahydrofuran, cyclohexanone and 2,3,4-tri-methoxy-benzaldehyde. Three non-classic hydrogen bonds were observed in the compound. X-ray crystallography shows that the crystal structure is stabilized by intermolecular C-H•••π interactions and it contains plenty of conjugated double bonds. The title compound was characterized by UV-vis and fluorescent spectral studies.

Preparation of symmetric dibromides of 1,10-phenanthroline

1997 ◽  
Vol 75 (10) ◽  
pp. 1336-1339 ◽  
Author(s):  
Yutaka Saitoh ◽  
Take-aki Koizumi ◽  
Kohtaro Osakada ◽  
Takakazu Yamamoto
Keyword(s):  
Molecular Structure ◽  
Aqueous Medium ◽  
Good Yield ◽  
X Ray ◽  
X Ray Crystallography

Bromation of 1,10-phenanthroline with Br2 proceeds smoothly in the presence of S2Cl2 and pyridine to give 3,8-dibromo-1,10-phenanthroline in good yield. Bromation of 2,9-dibutoxy-1,10-phenanthroline with Br2, in an aqueous medium gives 5,6-dibromo-2,9-dibutoxy-1,10-phenanthroline selectively. Similar bromination of 4,7-dibutoxy-1,10-phenanthroline with Br2 gives 3,8-dibromo-4,7-dibutoxy-1,10-phenanthroline, which forms a 1:1 adduct with Cu(NO3)2. Molecular structure of the 1:1 adduct has been determined by X-ray crystallography. Keywords: bromination, 1,10-phenanthroline, 3,8-dibromo-1,10-phenanthroline.

Effects of solvents on the crystal structure of cross-linked lysozyme crystals

2018 ◽  
Vol 32 (19) ◽  
pp. 1840041
Author(s):  
Yohei Yamada ◽  
Shota Toyama ◽  
Tomoki Yabutani
Keyword(s):  
Crystal Structure ◽  
Acetic Acid ◽  
Hydrochloric Acid ◽  
Dimethyl Sulfoxide ◽  
Optical Microscopy ◽  
Immersion Test ◽  
X Ray ◽  
Lattice Constants ◽  
X Ray Crystallography ◽  
Lysozyme Crystals

The effects of solvents on the structural stability of cross-linked lysozyme crystals were investigated by an immersion test using alkaline (0.1 M ammonia [NH3] and 0.1 M sodium hydroxide [NaOH]), acidic (0.1 M acetic acid [CH3COOH] and 0.1 M hydrochloric acid [HCl]) and organic (50% [v/v] and undiluted ethanol, acetone, 2-propanol and dimethyl sulfoxide [DMSO]) solvents. The morphology and lattice constants were monitored by optical microscopy and X-ray crystallography. The cross-linked crystals exhibited good stability against NH3, CH3COOH, HCl, ethanol, acetone and 2-propanol. However, samples preserved in DMSO and NaOH were severely degraded.

Direct Synthesis of 6H-Chromeno[3,4-b]quinolin-6-ol Derivatives from Substituted 3-Nitro-2H-chromenes and 2-Nitrobenzaldehydes Mediated by Fe/AcOH System

Synthesis ◽  
2017 ◽  
Vol 50 (06) ◽  
pp. 1350-1358 ◽  
Author(s):  
Cunde Wang ◽  
Xushun Qing ◽  
Ting Wang ◽  
Chenlu Dai ◽  
Zhenjie Su
Keyword(s):  
Acetic Acid ◽  
Nucleophilic Addition ◽  
Aldol Condensation ◽  
Direct Synthesis ◽  
Reductive Cyclization ◽  
Quinoline Derivatives ◽  
Acid System ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sequential Reduction

An efficient iron/acetic acid system-mediated reductive cyclization reaction of substituted 2-aryl-3-nitro-2H-chromenes with substituted 2-nitrobenzaldehydes for the synthesis of 6-aryl-6H-chromeno[3,4-b]quinolines was developed. This reaction involves the sequential reduction, hydrolysis, aldol condensation, intramolecular addition, and the nucleophilic addition of substituted 2-aryl-3-nitro-2H-chromenes with substituted 2-nitrobenzaldehydes to give the corresponding 6H-chromeno[3,4-b]quinolines. This transformation provides a straightforward synthetic protocol for constructing substituted 6H-chromeno[3,4-b]quinoline derivatives. The structures of three typical products were confirmed by X-ray crystallography.

scholarly journals A ferrocene redox-active triazolium macrocycle that binds and senses chloride

2012 ◽  
Vol 8 ◽  
pp. 246-252 ◽  
Author(s):  
Nicholas G White ◽  
Paul D Beer
Keyword(s):  
Solid State ◽  
Good Yield ◽  
Electrochemical Studies ◽  
Nmr Titration ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Redox Active

A ferrocene bis(triazole) macrocycle was synthesised in good yield by the Eglinton coupling of an acyclic bis(alkyne) precursor and characterised in the solid state by X-ray crystallography. Alkylation gives the corresponding triazolium macrocycle, which binds chloride and benzoate strongly in CD3CN solution through favourable charge-assisted C–H···anion interactions, as evidenced by 1H NMR titration experiments. Preliminary electrochemical studies reveal that the redox-active macrocycle is capable of sensing chloride in CH3CN solution.

Different solvents yield alternative crystal forms through aromatic, halogen bonding and hydrogen bonding competition

CrystEngComm ◽  
2015 ◽  
Vol 17 (4) ◽  
pp. 877-888 ◽  
Author(s):  
Solhe F. Alshahateet ◽  
Mohan M. Bhadbhade ◽  
Roger Bishop ◽  
Marcia L. Scudder
Keyword(s):  
Hydrogen Bonding ◽  
Acetic Acid ◽  
Halogen Bonding ◽  
Crystal Forms ◽  
X Ray ◽  
X Ray Crystallography ◽  
Protic Solvents

X-ray crystallography shows that entirely different structures are produced when the dichlorodiquinoline derivative is crystallised from aprotic dimethylformamide or from protic solvents like methanol or acetic acid, demonstrating the importance of solvent choice in yielding alternative crystal forms.

Preparation, Crystal Structure and Spectroscopic Characterization of [Ga(OH)(SO4)(terpy)(H2O)] · H2O (terpy=2,2’:6’,2-Terpyridine): The First Characterized Gallium(III) Sulfato Complex

2004 ◽  
Vol 59 (3) ◽  
pp. 291-297 ◽  
Author(s):  
Andreas Sofetis ◽  
Giannis S. Papaefstathiou ◽  
Aris Terzis ◽  
Catherine P. Raptopoulou ◽  
Theodoros F. Zafiropoulos
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Nmr Spectroscopy ◽  
Good Yield ◽  
Spectroscopic Data ◽  
Spectroscopic Characterization ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr

The reaction of Ga2(SO4)3·18H2O and excess 2,2′:6′,2″-terpyridine (terpy) in MeOH / H2O leads to [Ga(OH)(SO4)(terpy)(H2O)]·H2O (1·H2O] in good yield. The structure of the complex has been determined by single-crystal X-ray crystallography. The GaIII atom in 1·H2O is 6-coordinate and ligation is provided by one terdentate terpy molecule, one monodentate sulfate, one terminal hydroxide and one terminal H2O molecule; the coodination polyhedron about the metal is described as a distorted octahedron. There is an extensive hydrogen-bonding network in the crystal structure which generates corrugated layers parallel to bc. The new complex was characterized by IR and 1H NMR spectroscopy. The spectroscopic data are discussed in terms of the nature of bonding

scholarly journals Preparation of Pincer Hafnium Complexes for Olefin Polymerization

Molecules ◽  
2019 ◽  
Vol 24 (9) ◽  
pp. 1676 ◽  
Author(s):  
Su Jin Kwon ◽  
Jun Won Baek ◽  
Hyun Ju Lee ◽  
Tae Jin Kim ◽  
Ji Yeon Ryu ◽  
...  
Keyword(s):  
Olefin Polymerization ◽  
Ion Pair ◽  
Metallocene Catalysts ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pyridine Moiety ◽  
No Formation ◽  
Type Complex ◽  
Ligand Precursors

Pincer-type [Cnaphthyl, Npyridine, Namido]HfMe2 complex is a flagship among the post-metallocene catalysts. In this work, various pincer-type Hf-complexes were prepared for olefin polymerization. Pincer-type [Namido, Npyridine, Namido]HfMe2 complexes were prepared by reacting in situ generated HfMe4 with the corresponding ligand precursors, and the structure of a complex bearing 2,6-Et2C6H3Namido moieties was confirmed by X-ray crystallography. When the ligand precursors of [(CH3)R2Si-C5H3N-C(H)PhN(H)Ar (R = Me or Ph, Ar = 2,6-diisopropylphenyl) were treated with in situ generated HfMe4, pincer-type [Csilylmethyl, Npyridine, Namido]HfMe2 complexes were afforded by formation of Hf-CH2Si bond. Pincer-type [Cnaphthyl, Sthiophene, Namido]HfMe2 complex, where the pyridine moiety in the flagship catalyst was replaced with a thiophene unit, was not generated when the corresponding ligand precursor was treated with HfMe4. Instead, the [Sthiophene, Namido]HfMe3-type complex was obtained with no formation of the Hf-Cnaphthyl bond. A series of pincer-type [Cnaphthyl, Npyridine, Nalkylamido]HfMe2 complexes was prepared where the arylamido moiety in the flagship catalyst was replaced with alkylamido moieties (alkyl = iPr, cyclohexyl, tBu, adamantyl). Structures of the complexes bearing isopropylamido and adamantylamido moieties were confirmed by X-ray crystallography. Most of the complexes cleanly generated the desired ion-pair complexes when treated with an equivalent amount of [(C18H37)2N(H)Me]+[B(C6F5)4]−, which showed negligible activity in olefin polymerization. Some complexes bearing bulky substituents showed moderate activities, even though the desired ion-pair complexes were not cleanly afforded.

scholarly journals Comparison of the Photochemical Reaction of Photoactive Yellow Protein in Crystal with Reaction in Solution1

2003 ◽  
Vol 17 (2-3) ◽  
pp. 345-353 ◽  
Author(s):  
Eriko Mano ◽  
Hironari Kamikubo ◽  
Yasushi Imamoto ◽  
Mikio Kataoka
Keyword(s):  
Photochemical Reaction ◽  
Structural Changes ◽  
Spectroscopic Studies ◽  
Crystalline Lattice ◽  
Photoactive Yellow Protein ◽  
X Ray ◽  
X Ray Crystallography ◽  
Solution Condition ◽  
Active Intermediate ◽  
Ectothiorhodospira Halophila

Photoactive yellow protein (PYP) is a photoreceptor protein for the negative phototaxis ofEctothiorhodospira halophila. The crystal structures of several photo‒intermediates have been revealed by X-ray crystallography. In the crystal structure of the active intermediate, PYPM, no significant structural changes were observed except for the vicinity of the chromophore. On the contrary, spectroscopic studies with solution condition demonstrated that global structural changes occur during the photo‒cycle. In order to reveal the origin of the discrepancies, we measured the reaction kinetics upon illumination under crystal condition and to compare them with those observed under solution condition. The reactive portion decreases with the increase of crystallinity. The rate constant of PYPMdecay also decreases with the increase of crystallinity. These results suggest two possibilities: (1) PYP in crystal does not react by the illumination; (2) the photoreaction rate is highly accelerated in crystal. Consequently, the photoreaction in crystal is considered to be highly influenced by the force constraint from crystalline lattice.

New Coordination Polymers of Lanthanide(III) with Tetrazole-1-acetic Acid: Synthesis, Crystal Structures, and Magnetic Properties

2008 ◽  
Vol 61 (4) ◽  
pp. 303 ◽  
Author(s):  
Xiu-Qing Zhang ◽  
Qing Yu ◽  
He-Dong Bian ◽  
Shi-Ping Yan ◽  
Dai-Zheng Liao ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Coordination Polymers ◽  
Coordination Mode ◽  
Magnetic Measurements ◽  
Acid Synthesis ◽  
Antiferromagnetic Coupling ◽  
Bidentate Coordination ◽  
X Ray ◽  
X Ray Crystallography ◽  
Lanthanide Cations

New coordination polymers {[Ln(tza)3(H2O)2]·mH2O}n (Ln = LaIII 1 and PrIII 2, m = 2; Ln = NdIII 3, m = 1.5) and {[Sm2(tza)6(H2O)5]·H2O}n 4 (Htza = tetrazole-1-acetic acid) have been synthesized and characterized by IR spectroscopy, elemental analysis, X-ray crystallography, and magnetic measurements. The Htza ligand coordinates to the lanthanide cations through the carboxylate group in a monodentate, bridging bidentate coordination mode or bridging tridentate to two metal centres. Complexes 1 and 2 are isostructural. Complex 3 has a similar structure to 1 and 2, but the arrangement of ligands has changed. Complex 4 consists of two types of metallic molecules. Magnetic measurements show weak antiferromagnetic coupling between the metal centres in complexes 2 and 3.

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