Structural Characterization Of Rh(Iii) Complexes Containing The Polypyridyl Ligands And Some Properties Of Their Derivatives

2001 ◽  
Vol 56 (8) ◽  
pp. 747-752 ◽  
Author(s):  
Mee Y. Kim ◽  
Won K. Seok ◽  
Heung N. Lee ◽  
Sung H. Han ◽  
Yongkwan Dong ◽  
...  
Keyword(s):  
X Ray Diffraction ◽  
Chloride Complexes ◽  
Polypyridyl Ligands ◽  
X Ray ◽  
H Nmr ◽  
Rhodium Chloride ◽  
Nmr Data ◽  
Elemental Analyses ◽  
Rhodium Atom

The structures of the compounds [Rh(bpy)2(py)(Cl)](ClO4 )2 (2 (ClO4 )2) and [Rh(phen)2(py)- (Cl)](ClO4 )2 (7 -(ClO4 )2) were determined by single-crystal X-ray diffraction. Both complexes show a six-coordinate rhodium atom with two bpy or phen ligands in the cis configuration. The Rh-Cl distances are 2.334(3) and 2.323(2) Å, respectively. The bond angles N-Rh-Cl formed with the axially-positioned nitrogen atom are 174.4(2) and 173.8(2)°. The oxidation of aquo complexes, prepared from the corresponding rhodium chloride complexes, by two equivalents of Ce(IV) in 60% HCIO4 solution yields the corresponding mono-oxo products. All complexes have been identified and characterized by elemental analyses, IR, and 1H NMR data

Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids

1993 ◽  
Vol 48 (4) ◽  
pp. 409-417 ◽  
Author(s):  
Rostislav D. Lampeka ◽  
Zamira D. Uzakbergenova ◽  
Victor V. Skopenko
Keyword(s):  
Electronic Absorption Spectra ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
R Factors

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.

Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads

2018 ◽  
Vol 22 (09n10) ◽  
pp. 814-820
Author(s):  
Yingying Jia ◽  
Ling Xu ◽  
Bangshao Yin ◽  
Mingbo Zhou ◽  
Jianxin Song
Keyword(s):  
Nickel Complex ◽  
High Resolution Mass Spectrometry ◽  
Dihedral Angles ◽  
X Ray Diffraction ◽  
Extinction Coefficients ◽  
X Ray ◽  
H Nmr ◽  
First Time ◽  
Molar Extinction Coefficients

Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier–Haack reaction, condensation with pyrrole, bromination with [Formula: see text]-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metal-templated cyclization of dibromodipyrrin-metal complexes with NaN[Formula: see text] and demetalization. All these triads were comprehensively characterized by [Formula: see text]H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)[Formula: see text] between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.

Preparation and characterization of some ruthenium(II) porphyrins containing tertiary phosphine axial ligands, including the crystal structure of (octaethylporphinato)bis(triphenylphosphine)ruthenium(II)

1984 ◽  
Vol 62 (4) ◽  
pp. 755-762 ◽  
Author(s):  
Sara Ariel ◽  
David Dolphin ◽  
George Domazetis ◽  
Brian R. James ◽  
Tak W. Leung ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Phosphine Ligands ◽  
Tertiary Phosphine ◽  
X Ray ◽  
Porphyrin Complex ◽  
H Nmr ◽  
Axial Ligands ◽  
Nmr Data ◽  
Phosphine Complex

The ruthenium(II) porphyrin complex Ru(OEP)(PPh3)2 (OEP = the dianion of octaethylporphyrin) has been prepared from Ru(OEP)(CO)EtOH, and the X-ray crystal structure determined; as expected, the six-coordinate ruthenium is situated in the porphyrin plane and has two axial phosphine ligands. Synthesized also from the carbonyl(ethanol) precursors were the corresponding tris(p-methoxyphenyl)phosphine complex, and the Ru(TPP)L2 (TPP = the dianion of tetraphenylporphyrin, L = PPh3, P(p-CH3OC6H4)3, P″Bu3) and Ru(TPP)(CO)PPh3 complexes. Optical and 1H nmr data are presented for the complexes in solution. In some cases dissociation of a phosphine ligand to generate five-coordinate species occurs and this has been studied quantitatively in toluene at 20 °C for the Ru(OEP)L2 and Ru(TPP)L2 systems.

β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes

2007 ◽  
Vol 62 (3) ◽  
pp. 475-482 ◽  
Author(s):  
Karsten Schubert ◽  
Helmar Görls ◽  
Wolfgang Weigand
Keyword(s):  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
H Nmr ◽  
Hexyl Ester ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.

Synthesis and Electrochemistry of Aluminum Porphycenes: Crystal and Molecular Structure of Methyl-σ-Bonded Aluminum Etioporphycene

1997 ◽  
Vol 01 (02) ◽  
pp. 109-119 ◽  
Author(s):  
ROGER GUILARD ◽  
VIRGINIE PICHON-PESME ◽  
HASSANE LACHEKAR ◽  
CLAUDE LECOMTE ◽  
ALLY M. AUKAULOO ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Structural Data ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Axial Ligands ◽  
Uv Visible

The synthesis and characterization of three monomeric aluminum porphycenes with anionic or σ-bonded axial ligands is reported. The investigated compounds are represented as ( EtioPc ) Al ( CH 3) and ( EtioPc ) AlX where EtioPc represents the dianion of etioporphycene and X = Cl − or OH −. Each synthesized complex was characterized by mass spectrometry. 1 H NMR, IR and UV-visible spectroscopies as well as by electrochemistry. Comparisons are made between the properties of complexes in the aluminum etioporphycene series and related chloro- or methyl σ-bonded Al ( III ) porphyrins containing octaethylporphyrin ( OEP ) or tetraphenylporphyrin ( TPP ) macrocycles. Comparisons are also made between the currently investigated compounds and a previously reported Al ( III ) μ-oxo dimer, [( EtioPc ) Al ]2 O . In addition, the crystal and molecular structure of ( EtioPc ) Al ( CH 3) was determined by X-ray diffraction. The molecular structure of this methyl-σ-bonded aluminum etioporphycene provides the first structural data for an aluminum porphycene compound. The aluminum(III) atom in ( EtioPc ) Al ( CH 3) is pentacoordinated and is located 0.54 Å from the plane of the four N -nitrogens.

Synthesis and Structural Characterization of a Series of Group 11 2,2-Dialkyl-1,3-dicyclohexylguanidinate Complexes

2014 ◽  
Vol 67 (7) ◽  
pp. 1021 ◽  
Author(s):  
Sonya K. Adas ◽  
Jesus A. Ocana ◽  
Scott D. Bunge
Keyword(s):  
Fourier Transform ◽  
Infrared Spectroscopy ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
X Ray ◽  
7Li Nmr ◽  
Elemental Analyses ◽  
Lithium Diethylamide ◽  
Structural Aspects

The addition of either lithium dimethylamide or lithium diethylamide to a tetrahydrofuran (THF) solution of 1,3-dicyclohexylcarbodiimide yielded THF adducts of lithium 2,2-dimethyl-1,3-dicyclohexylguandidinate (1) and lithium 2,2-diethyl-1,3-dicyclohexylguandidinate (2), respectively. One equivalent of either 1 or 2 was subsequently reacted with one equivalent of Group 11 halide (CuCl, AgBr, and AuCl) to generate oligonuclear complexes with the general formula {M[CyNC(NR2)NCy]}n where M, R, and n are respectively Cu, CH3, 2 (3); Cu, CH2CH3, 2 (4); Ag, CH3, 3 (5); Ag, CH2CH3, 3 (6); Au, CH3, 2 (7); and Au, CH2CH3, 2 (8). Compounds 1–8 were characterized by single-crystal X-ray diffraction. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, Fourier transform infrared spectroscopy, and 1H, 13C, and 7Li NMR studies. The unique structural aspects of this family of Group 11 complexes are highlighted.

Synthesis and Characterization of a Dumbbell-Shaped Polyrotaxane Based on Polytetrahydrofuran bis(3-aminopropyl) Terminated and α-Cyclodextrins Using Polyamidoamine (PAMAM) Dentrimers as Bulky Stoppers

2015 ◽  
Vol 1094 ◽  
pp. 41-48
Author(s):  
Ri Min Cong ◽  
Huai Qing Yu ◽  
Yan Gong Yang ◽  
Si Yi Yang ◽  
Jiao Li ◽  
...  
Keyword(s):  
Thermogravimetric Analysis ◽  
Inclusion Complex ◽  
Inclusion Complexes ◽  
Synthesis And Characterization ◽  
Wide Angle ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Channel Type

A dumbbell-shaped polyrotaxane based on polytetrahydrofuran bis (3-aminopropyl) terminated and α-cyclodextrins using polyamidoamine (PAMAM) dentrimers as bulky stoppers was successfully prepared. The1H NMR results show that the peaks of α-CDs in these polyrotaxanes are broadened compared with pure α-CDs. Wide-angle X-ray diffraction (XRD) measurements of the resulting polyrotaxanes suggest to produce a channel-type crystalline structure of inclusion complex. Thermogravimetric analysis (TGA) of the resultant polyrotaxanes show that α-CDs are significantly stabilized by the formation of the inclusion complexes.

scholarly journals Lactide polymerization with iron alkoxide complexes

2015 ◽  
Vol 93 (6) ◽  
pp. 594-601 ◽  
Author(s):  
Arek Keuchguerian ◽  
Berline Mougang-Soume ◽  
Frank Schaper ◽  
Davit Zargarian
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Side Reactions ◽  
X Ray Diffraction ◽  
Iron Cluster ◽  
X Ray ◽  
H Nmr ◽  
Exchange Product

This report presents the results of a study on the preparation of iron alkoxide complexes chelated by diiminopyridine ligands and their role in the room temperature polymerization of rac-lactide. Reaction of N,N′-(p-R-C6H4CH2)2-diiminopyridines (R = H (1), F (2)) with FeX2 (X = Cl, Br) yielded the homoleptic complexes [(1)2Fe][FeX4] or [(2)2Fe][FeX4], respectively. Treating the latter with Na[BPh4] afforded the anion exchange product [(2)2Fe][BPh4]2, which was characterized by 1H NMR and absorption spectroscopy, combustion analysis, and single crystal X-ray diffraction. Various attempts to grow crystals of [(1)2Fe][FeX4] and [(2)2Fe][FeX4] culminated in the isolation of single crystals of [(2)2Fe][Cl6Fe2O] that was characterized by X-ray diffraction. Attempted synthesis of well-defined, mononuclear alkoxide derivatives from [(1)2Fe]2+ or [(2)2Fe]2+ gave mostly intractable products, but in one case we obtained the crystallographically characterized sodium iron cluster Na4Fe2(OC6H4F)8(THF)2. An aryloxide derivative proved accessible by reaction of NaOC6H4F with the mono-ligand precursor LFeCl2 (L = N,N′-dimesityl-diiminopyridine), but characterization of LFe(OC6H4F)2 was limited to a single crystal X-ray diffraction analysis, owing to unsuccessful attempts at isolating pure samples. The difficulties encountered in the isolation of pure alkoxide derivatives prompted us to use in-situ generated LFe(OEt)2 for studying the polymerization of rac-lactide. This system was found to be moderately active at room temperature and with a slight preference for the formation of a heterotactic polymer (Pr = 0.54–0.65). Large polydispersities of 1.5–2.0 indicated the presence of transesterification side-reactions, which were confirmed by the presence of peaks with m/z = n 144 + M(EtOH) + M(Na+) and m/z = (n + 0.5) 144 + M(EtOH) + M(Na+) in MALDI-MS.

Structure of isosilerolide, relative and absolute configuration of silerolide and lasolide - Sesquiterpenic lactones of new stereoisomeric type of eudesmanolides

1986 ◽  
Vol 51 (4) ◽  
pp. 903-929 ◽  
Author(s):  
Miroslav Holub ◽  
Miloš Buděšínský ◽  
Zdenka Smítalová ◽  
David Šaman ◽  
Urszula Rychłewska
Keyword(s):  
Absolute Configuration ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
Chemical Correlation ◽  
The Absolute

On the basis of spectroscopic, particularly 1H NMR data, isosilerolide was assigned structure I, including the absolute configuration. The structure was confirmed by X-ray diffraction. Isosilerolide represents a new stereoisomeric type of natural eudesmanolides, characterized as 5βH, 6αH, 7αH, 10αCH3-eudesman-6,12-olide. As shown by the chemical correlation of isosilerolide (I) with silerolide (III) and lasolide (X), the latter two natural lactones belong to this stereoisomeric group of eudesmanolides. Analysis of models and 1H NMR data shows that structures of some eudesman-6,12-olides, published by other authors, should be corrected.

On Attempts to Synthesize Lanthanide Complexes of the Dianionic Fluorenyl-alkoxo Ligand [C13H8-cyclo-C6H10-O]2-. Crystal Structure of (C13H9-cyclo-C6H10-O)LaI2(DME)2

2003 ◽  
Vol 58 (5) ◽  
pp. 389-394 ◽  
Author(s):  
Alexander A. Trifonov ◽  
Mikhail N. Bochkarev ◽  
Herbert Schumann ◽  
Sebastian Dechert
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Ir Spectra ◽  
Single Crystal ◽  
Lanthanide Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Elemental Analyses ◽  
C Nmr

Racemic trans-2-(9(H)-fluoren-9-yl)cyclohexanol, C13H9-cyclo-C6H10-OH (1), reacts with two equivalents of potassium naphthalenide in THF to give the dipotassium salt [C13H8-cyclo-C6H10-O]- K2(THF) (2). Recrystallization of 2 from pyridine affords the solvent free salt [C13H8-cyclo-C6H10- O]K2 (3). The reactions of LaI3(THF)4 with one equivalent of 2 or of YbI2(THF)2 with equimolar amounts of 2 produce the alkoxolanthanum diiodide (C13H9-cyclo-C6H10-O)LaI2(DME)2 (4) and the ytterbium dialkoxide (C13H9-cyclo-C6H10-O)2Yb(THF)0.5(5), respectively. [(Me3Si)2N]3Y reacts with three equivalents of 1 with elimination of hexamethyldisilazane and formation of the yttrium trialkoxide (C13H9-cyclo-C6H10-O)3Y (6). The compounds 2 to 5 were characterized by elemental analyses, 1H NMR, 13C NMR and IR spectra. The molecular structure of 4 was determined by single crystal X-ray diffraction.

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