Synthesis and NMR characterization of the cis and trans isomers of [Ptii(N9-adeH)2(pz)2] and X-ray crystallography of the trans isomer

2007 ◽  
pp. 3966 ◽  
Author(s):  
Karel D. Klika ◽  
Henri Kivelä ◽  
Vladimir V. Ovcharenko ◽  
Ville Nieminen ◽  
Reijo Sillanpää ◽  
...  
Keyword(s):  
Trans Isomer ◽  
Trans Isomers ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cis And Trans Isomers ◽  
Nmr Characterization ◽  
Cis And Trans

Syntheses, electrochemistry and photophysical properties of a series ofmeso-pyridylpentafluorophenylporphyrins

2010 ◽  
Vol 14 (11) ◽  
pp. 975-984 ◽  
Author(s):  
Emmanuel Z. Moreira ◽  
Alba D.Q. Ferreira ◽  
Cláudio Roberto Neri ◽  
Sumitra Mukhopadhyay ◽  
Sérgio Dovidauskas ◽  
...  
Keyword(s):  
Electrochemical Properties ◽  
Photophysical Properties ◽  
Synthesis And Characterization ◽  
Redox Potentials ◽  
Trans Isomers ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cis And Trans Isomers ◽  
Cis And Trans

This work presents the synthesis and characterization of a series of substituted pyridylpentafluroporphyrins, including the separation of the cis- and trans-isomers, the latter being characterized by X-ray crystallography. The spectroscopic and electrochemical properties of the series are dependent on the number of electron withdrawing pentafluorophenyl substituent, but they do not depend on the symmetry of the molecule. Ongoing from the monosubstituted to the more substituted pentafluorophenyl porphyrin H2(MPyTFPP) derivative, the Soret bands are slightly red-shifted and their quantum fluorescence yields range from 0.035 to 0.046, consistent with the value of 0.045 for the fully substituted 5,10,15,20-tetrapentafluorophenylporphyrin (dichloromethane solutions). The redox potentials of the reductive processes of monoanion and dianion formation are also sensitive to the number of pentafluoro substituents, shifting 180 mV to more positive values for the P0/P-1process ongoing from the monopentafluoro to the tris-pentafluorophenyl substituted derivative.

Synthesis and characterization of cis and trans isomers of [NiL2(NCS)2] [L=1-(2-aminoethyl)pyrrolidine]: X-ray single-crystal structures

Polyhedron ◽  
2000 ◽  
Vol 19 (15) ◽  
pp. 1803-1807 ◽  
Author(s):  
Inamur Rahaman Laskar ◽  
Tapas Kumar Maji ◽  
Siddhartha Chaudhuri ◽  
Ashutosh Ghosh ◽  
Nirmalendu Ray Chaudhuri
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Synthesis And Characterization ◽  
Trans Isomers ◽  
X Ray ◽  
Single Crystal Structures ◽  
Cis And Trans Isomers ◽  
Cis And Trans

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd2I2(µ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(µ-Ppy3)2(µ-MeO2C•C=C•CO2Me); py = 2-pyridyl

1992 ◽  
Vol 70 (3) ◽  
pp. 751-762 ◽  
Author(s):  
Yun Xie ◽  
Chung-Li Lee ◽  
Yeping Yang ◽  
Steven J. Rettig ◽  
Brian R. James
Keyword(s):  
Palladium Complexes ◽  
Monoclinic Space Group ◽  
Trans Isomers ◽  
Space Group ◽  
X Ray ◽  
Mononuclear Complexes ◽  
Cis And Trans Isomers ◽  
Pyridylphosphine Ligands ◽  
Cis And Trans

Dibromo- and diiodo[(2-pyridyl)phosphine]palladium(II) complexes are prepared by metathesis of cis-PdCl2(PPh3−npyn)2 species (n = 1–3) using the appropriate sodium halide; py = 2-pyridyl. NMR spectroscopy, particularly,13C{1H}, is used to distinguish cis and trans isomers. The dinuclear complexes Pd2X2(μ-PPh3−npyn)2, X = halide, are synthesized via a conproportionation reaction using PdX2(PPh3−npyn)2 and Pd2(dba)3; dba = dibenzylideneacetone. Both Pd2l2(μ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(μ-Ppy3)2(μ-MeO2C•C=C•CO2Me) are characterized crystallographically as head-to-tail isomers. The former crystallizes in the monoclinic space group C2/c with a = 30.992(3), b = 18.764(1), c = 13.100(1) Å, β = 100.676(5)°, and Z = 8; the data were refined to R = 0.035 for 5874 reflections with I ≥ 3σ(I). The A-frame compound is triclinic of space group [Formula: see text] with a = 13.545(2), b = 15.064(2), c = 11.991(2) Å, α = 111.56(1), β = 95.36(1), γ = 97.63(1)°, and Z = 2; R = 0.033 from 7128 reflections with I ≥ 3σ(I). The Pd2X2(μ-PPhpy2)2 complexes exist as a mixture of diastereomers because of chirality induced at the phosphorus atoms. The Pd2X2(μ-Ppy3)2 complexes in water generate the [Pd2(H2O)2(μ-Ppy3)2]2+ dication, which is isolated as various salts. The mononuclear complexes in water generate aquo and hydroxo species. Keywords: dimethylacetylenedicarboxylate adducts, palladium complexes (dinuclear), pyridylphosphines.

Gold complexes of ditelluridoimidodiphosphinate ligands — Reversible oxidation of Au(I) to Au(III) via insertion of gold into a phosphorus–tellurium bond

2009 ◽  
Vol 87 (1) ◽  
pp. 39-46 ◽  
Author(s):  
Dana J Eisler ◽  
Stuart D Robertson ◽  
Tristram Chivers
Keyword(s):  
Solid State ◽  
Solid State Nmr ◽  
Trans Isomers ◽  
Nmr Studies ◽  
Gold Complexes ◽  
X Ray ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Insertion Process

The reaction of (THT)AuCl with (TMEDA)Na[N(TePR2)2] (R = Ph, i-Pr, t-Bu) produces a series of gold (III) complexes of the type [{R2PNP(Te)R2}Au(µ-Te)]2 (4a, R = i-Pr; 4b, R = Ph; 4c, R = t-Bu) rather than the expected homoleptic Au(I) complexes of the ditelluridoimidodiphosphinate ligands. A combination of solution- and solid-state NMR studies shows that both cis and trans isomers of 4a–4c are formed in these reactions. X-ray structural determinations of the trans isomers of 4a–4c reveal a centrosymmetric arrangement with a central four-membered Au2Te2 ring formed by the formal insertion of gold into a P–Te bond; this insertion process was shown to be reversible upon addition of PPh3 to 4a to give the monomeric gold(I) complex Ph3PAu[N{TeP(i-Pr)2}2]. The X-ray structure of cis-4b is also described.Key words: gold, tellurium, redox, X-ray structures, imidodiphosphinate.

Synthesis, isolation, and characterization of the cis and trans isomers of steroidal 20-hydroxy-17(20)-en-21-aldehydes

1989 ◽  
Vol 54 (6) ◽  
pp. 1332-1338 ◽  
Author(s):  
Marvin L. Lewbart ◽  
Carl Monder ◽  
Walter J. Boyko ◽  
Carol J. Singer ◽  
F. Iohan
Keyword(s):  
Trans Isomers ◽  
Isolation And Characterization ◽  
Cis And Trans Isomers ◽  
Cis And Trans

Sur la réduction de polyméthyldihydro-2,3 phénalènones-1 par l'hydrure de lithium et d'aluminium

1974 ◽  
Vol 52 (17) ◽  
pp. 3106-3112 ◽  
Author(s):  
E. Costakis ◽  
P. Canonne ◽  
R. St-Jean
Keyword(s):  
Trans Isomer ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Considerable Extent ◽  
Lithium Aluminum ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
Cis Isomer ◽  
Steric Constraints

The reduction of some polymethyl-2,3-dihydro phenalen-1-ones by lithium aluminum hydride yields a mixture of cis and trans isomers; the percentage of each isomer depends to a considerable extent on its structure. Indeed, for some, the trans isomer predominates while for others the cis isomer is obtained in up to 88% yields. Moreover, in the particular case in which the trans isomer is formed in low yields, its preferred conformation is trans diaxial.The steric constraints which render certain transition states unfavourable during the attack of the hydride are discussed with the aid of spectroscopic data on the alcohols obtained. [Journal translation]

SYNTHESES IN THE TERPENE SERIES: VIII. SYNTHESIS OF THE CIS- AND TRANS-ISOMERS OF 7,7,10-TRIMETHYLDECAL-1-ONE. A CONVENIENT MODIFICATION OF THE BROWN HYDRATION REACTION

1959 ◽  
Vol 37 (11) ◽  
pp. 1870-1880 ◽  
Author(s):  
Franz Sondheimer ◽  
Saul Wolfe
Keyword(s):  
Trans Isomer ◽  
Raney Nickel ◽  
Equilibrium Mixture ◽  
Hydration Reaction ◽  
Trans Isomers ◽  
Perbenzoic Acid ◽  
Cis And Trans Isomers ◽  
Cis And Trans

7,7,10-Trimethyl-Δ1(9)-octal-2-one (VII) was converted to the cycloethylenedithioketal (VIII), which on Raney nickel reduction yielded 7,7,10-trimethyl-Δ1(9)-octalin (IX). Oxidation with perbenzoic acid led to the corresponding oxide (X), which could be rearranged in low yield to an equilibrium mixture of 7,7,10-trimethyldecal-1-one consisting essentially of the trans-isomer (XI).A convenient modification of the Brown hydration reaction is described, whereby the necessity of generating diborane or of using diglyme is avoided. 7,7,10-Trimethyl-Δ1(9)-octalin (IX) on Brown hydration using this modification stereospecifically furnished 7,7,10β-tri-methyl-cis-decal-1β-ol (XII), which was oxidized to 7,7,10-trimethyl-cis-decal-1-one (XIII). Isomerization resulted in the above-described equilibrium mixture containing at least 90% of the trans-isomer (XI). Similarly, the previously described 10-methyl-Δ1(9)-octalin (XVI) yielded a mixture of the cis- and trans-isomers of 10-methyldecal-1-one (XIX). Syntheses of 2-methylene-7,7,10-trimethyl-Δ1(9)-octalin (XIV) and of 7,7,10-trimethyl-cis-decal-2,3-dione 3-dithiotrimethylene ketal (XXII) are also described.

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