Preparation and characterization of some ruthenium(III) porphyrins, including the crystal structure of bromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)

1984 ◽  
Vol 62 (7) ◽  
pp. 1239-1245 ◽  
Author(s):  
Brian R. James ◽  
David Dolphin ◽  
T. W. Leung ◽  
Frederick W. B. Einstein ◽  
Anthony C. Willis
Keyword(s):  
Crystal Structure ◽  
Cation Radical ◽  
Hydrogen Halides ◽  
X Ray ◽  
Radical Intermediates ◽  
H Nmr ◽  
Nmr Data ◽  
Paramagnetic Shifts

Some ruthenium(III) complexes Ru(porp)(L)X and [Ru(porp)L2]X, (porp = dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP); L = PPh3, P″Bu3; X = Br, Cl) have been prepared from the precursor complexes Ru(porp)L2 or Ru(porp)(CO)L using as oxidant the halogens, or air in the presence of the hydrogen halides. The X = PF6 salts can be made using Et3O+PF6− as oxidant. Ruthenium(II) porphyrin π-cation radical intermediates have sometimes been detected. The X-ray crystal structure of Ru(OEP)(PPh3)Br, the first reported for a ruthenium(III) porphyrin, reveals that metal is displaced 0.049 Å from the plane of the pyrrole N atoms towards the phosphine. The Ru(OEP)(py) Br and [Ru(OEP)(py)CH3CN]PF6 complexes have been synthesized from Ru(OEP)(CO)py. The ruthenium(III) complexes are low-spin as shown by magnetic and esr data. Optical and 1H nmr data, the latter showing large paramagnetic shifts, are also presented.

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.

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.

Oxazoline chemistry — Part IV: Synthesis and characterization of oxazoline complexes of the zinc halides

2003 ◽  
Vol 81 (12) ◽  
pp. 1482-1491 ◽  
Author(s):  
Tosha M Barclay ◽  
Ignacio del Río ◽  
Robert A Gossage ◽  
Sarah M Jackson
Keyword(s):  
Crystal Structure ◽  
Structural Diversity ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
Zinc Compounds ◽  
X Ray ◽  
H Nmr ◽  
Oxazoline Ligands

The synthesis and characterization of 11 zinc halide derivatives that contain monodentate oxazoline ligands is described. The treatment of ether solutions of [ZnX2] (X = Cl, Br, I) with 2-aryl- or 2-methyl-2-oxazolines results in the formation of mildly hygroscopic complexes of the general formulae [ZnX2(ox)2] (ox = 2-methyl-2-oxazoline (1), 2,4,4-trimethyl-2-oxazoline (2), 2-phenyl-2-oxazoline (3), or 4,4-dimethyl-2-phenyl-2-oxazoline (4)), except in the case of ZnI2, which does not form an isolable complex — likely for steric reasons — with oxazoline 4. Treatment of [ZnBr2(4)2] with 1 reveals (1H NMR) that 1 only sluggishly displaces coordinated 4 at temperatures below 50 °C. The structural characterization, via single crystal X-ray diffraction, of six of the complexes, viz. [ZnI2(1)2], [ZnI2(2)2], [ZnX2(3)2] (X = Cl, Br, or I), and [ZnBr2(4)2], is also reported. All of these structurally characterized complexes are mononuclear zinc compounds with an overall distorted tetrahedral arrangement of the two halide and two oxazoline ligands around the zinc metal centre. The oxazoline series of complexes reported herein show little structural diversity, a facet which is in contrast to their substituted pyridine analogues.Key words: oxazoline, zinc, X-ray crystal structure, coordination complex, NMR spectroscopy, Zn(II).

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

Synthesis and characterization of a hexaphyrin(1.0.1.0.0.0) bearing both meso- and β-substituents

2007 ◽  
Vol 11 (04) ◽  
pp. 287-293 ◽  
Author(s):  
Jonathan L. Sessler ◽  
Patricia J. Melfi ◽  
Vincent M. Lynch
Keyword(s):  
Crystal Structure ◽  
Ring Current ◽  
Spectroscopic Studies ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Planar Conformation ◽  
Hydrogen Bound

The synthesis of an isoamethyrin-type expanded porphyrin bearing both meso- and β-substituents is presented. The diprotonated form of this macrocycle was characterized by conventional spectroscopic means and via a single crystal X-ray diffraction analysis. This species is observed to adopt a planar conformation in the solid state. Nonetheless, the inner ring current, as inferred from 1 H NMR spectroscopic studies, is found to be severely diminished as compared to isoamethyrin, by the presence of the two meso-phenyl moieties. A second crystal structure, in which a molecule of water is hydrogen-bound to a pyrrole NH , was also solved.

Complexes of methylmercury(II) with 1-methylcytosine and crystal structure of μ-(1-methylcytosinato-N3,N4)bis(methylmercury(II)) nitrate

1981 ◽  
Vol 59 (15) ◽  
pp. 2290-2297 ◽  
Author(s):  
Leonardo Prizant ◽  
Roland Rivest ◽  
André L. Beauchamp
Keyword(s):  
Crystal Structure ◽  
Amino Group ◽  
Nitrate Salt ◽  
Acidic Media ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
H Nmr ◽  
R Factor ◽  
Nmr Data ◽  
Solid Complexes

Two types of solid complexes are isolated by reaction of CH3HgX (X = NO3 and ClO4) with 1-methylcytosine (MCy). The CH3Hg+ ion is probably bonded to N(3) in the [CH3Hg(MCy)]X compounds. Mercury binding to N(3) and the deprotonated amino group in [(CH3Hg)2(MCy—H)]X is confirmed by X-ray work on the nitrate salt. The crystals are orthorhombic, space group Pbca, with a = 12.014, b = 13.573, c = 16.353 Å, and Z = 8. The structure was refined on 962 independent reflections to an R factor of 0.038. The CH3Hg+ groups are arranged in a syn configuration and the angles around the mercury-bonded nitrogen atoms are severely distorted to prevent short Hg … Hg contacts. N(3)-coordination in the 1:1 complexes introduces minor changes in the infrared spectra, but the substitution of an amino proton in the 1:2 compounds produces important modifications. 1H nmr data in DMSO-d6 are reported for both types of compounds. This work emphasizes the important acidity enhancement experienced by the amino protons upon initial coordination to N(3), which facilitates further reaction of CH3Hg+ by proton displacement even in acidic media.

Preparation and characterization of a new type of symmetrical dicyclopentyl substituted cucurbit[6]uril

2021 ◽  
pp. 095400832110231
Author(s):  
Jun Zheng ◽  
Lin Zhang ◽  
Xinan Yang ◽  
Ye Meng ◽  
Yanmei Jin ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrochloric Acid ◽  
Honeycomb Structure ◽  
Monoclinic Crystal System ◽  
Monoclinic Crystal ◽  
X Ray ◽  
H Nmr ◽  
Group A ◽  
New Type

A symmetrical dicyclopentyl substituted cucurbit[6]uril (CyP2Q[6]) was synthesized, and crystallized under the conditions of 3 mol/L hydrochloric acid solution and the induction of ZnCl2. The crystal structure was characterized by X-ray single crystal diffractometer, 1H NMR and MS, and the results show that the crystal belongs to the monoclinic crystal system with P21/n space group, a = 13.095 (2), b = 33.002 (6), c = 15.770 (3), α = 90°, β = 102.828(5)°, γ = 90°, Z = 4, and a macroporous honeycomb structure appears in the crystal.

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

Preparation and Structural Characterization of Methylmercury(II) Complexes of 5-Aza- and 6-Azauracil Derivatives

1987 ◽  
Vol 42 (12) ◽  
pp. 1556-1562 ◽  
Author(s):  
W. S. Sheldrick ◽  
S. Heeb
Keyword(s):  
Structural Analysis ◽  
Binding Sites ◽  
Ionic Complex ◽  
X Ray ◽  
H Nmr ◽  
Ph Values ◽  
Nmr Data ◽  
Wide Ph Range ◽  
Ph Range

Abstract1:1 Methylmercury(II) complexes of the anti-tumour agent 6-azauracil (6AUH2) and its deriva­tives 6-azathymine (6ATH2). 1-methyl-6-azauracil (6AMUH) and 1-methyl-6-azathymine (6AMTH) have been isolated from aqueous solutions of CH3HgOH and the respective base. N3-Coordination was established by X-ray structural analysis for both [(CH3Hg)6 AUH] (1) (pH 6-8) and [(CH3Hg)6 AMT] (5) (pH 4-12); in addition 1H NMR data are in accordance with an identical binding site in the complexes [(CH3Hg)6AMU] (3) and [(CH3Hg)6 ATH] (4). Using an excess of CH3HgOH. 2:1 complexes with N1, N3-coordination may be prepared for both 6 AUH: and 5 AUH2 in a wide pH range (4-12 and 6-12 respectively). At pH values of 3-4 a 3:1 complex [(CH3Hg)35 AU]NO3 (7), with N1, N3, N5-coordination may be isolated: the binding sites were confirmed by X-ray structural analysis. In no case could an ionic complex with N6- coordination be isolated for a 6-azapyrimidine derivative. The binding preferences of the bases are discussed in the light of MNDO calculations.

Structural characterization of Cd3(O3PC2H4CO2)2·2H2O from in-house X-ray powder data and NMR

2005 ◽  
Vol 61 (6) ◽  
pp. 669-674 ◽  
Author(s):  
Naima Bestaoui ◽  
Xiang Ouyang ◽  
Florence Fredoueil ◽  
Bruno Bujoli ◽  
Abraham Clearfield
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Structural Characterization ◽  
Title Compound ◽  
Solid State Nmr ◽  
Hydrothermal Reaction ◽  
X Ray ◽  
Space Groups ◽  
Nmr Data

The title compound poly[[bis(μ-2-carboxylatoethylphosphonato)cadmium] dihydrate], Cd3(O3PC2H4CO2)2·2H2O, was prepared by a hydrothermal reaction and its crystal structure determined from in-house powder data. The structure was solved in both P21/c and P21 space groups. The refinement converged with Rp = 0.1046, R wp = 0.1378 and Rf = 0.0763 in P21/c. However, the solid-state NMR data could not be explained. The structure was then solved in P21 and the refinement converged with Rp = 0.0750, R wp = 0.1022 and Rf = 0.0409 and satisfied the NMR requirements.

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