Polarography of some coordination compounds of Platinum. III. Ions of the tetrammineplatinum(II) type

1956 ◽  
Vol 9 (1) ◽  
pp. 14 ◽  
Author(s):  
JR Hall ◽  
RA Plowman

A number of tetrammine ions of divalent platinum, in which the ligands were ammonia, methylamine, dimethylamine, ethylenediamine, pyridine, aniline, and combinations of some of these, were studied at the dropping mercury electrode. Some of the ions showed maxima in their current-voltage curves (c-v curves). The formation of hydrogen interfered with the c-v curves of other ions, so that limiting currents were not obtainable. A method was devised for the measurement of a voltage by means of which the ease of reduction of the ions could be compared. Using a supporting electrolyte of 0.1M KCl and 0.01% gelatin, the order of increasing ease of reduction was found to be [Pt{(CH3)2NH)4]2+ = [Pt(NH3)4]2+ = [Pt(NH3)3(C5H5N)]2+ = [Pt{C2H4(NH2)2}2]2+ < cis-[Pt(NH3)2(C5H5N)2]2+ < trans-[Pt(NH3)2C5H5N)2]2+ < [Pt(CH3NH2)4]2+ = [Pt(NH3)(C5H5N)3]2+ <[Pt(C6H5N)4]2+ < cis-[Pt(NH3)2(C6H5NH2)2]2+ < trans-[Pt(NH3)2(C6H5NH2)2]2+. When the ammonia groups of [Pt(NHS),l2+ were successively replaced by pyridine groups, the resulting e-v curves shifted progressively to more positive voltages. It was also found that cis- and trans-isomers of [PtA,B,I2+ reduced at different voltages. The trans-isomer reduced more readily.


1974 ◽  
Vol 52 (17) ◽  
pp. 3106-3112 ◽  
Author(s):  
E. Costakis ◽  
P. Canonne ◽  
R. St-Jean

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]



1956 ◽  
Vol 9 (2) ◽  
pp. 143 ◽  
Author(s):  
JR Hall ◽  
RA Plowman

Four ions were studied at the dropping mercury electrode. They were [Pt(ophen)2]2+, [Pt(ophen)(en)]2+, [Pt(ophen)(py)2]2+, and [Pt(ophen)(py)Cl]+, where ophen= 1,10- phenanthroline, en=ethylenediamine, and py=pyridine. The shapes of the c-v curves of the ions in supporting electrolyte 0.1M KCl, were dependent on complex ion concentration. Adsorption phenomena occurred with some ions but the effects decreased as the complex ion concentration decreased. The reduction of [Pt(ophen)2]2+ produced evidence for compounds of platinum with valency less than two. Reduction of the other ions appeared to proceed directly to metallic platinum.



1959 ◽  
Vol 37 (11) ◽  
pp. 1870-1880 ◽  
Author(s):  
Franz Sondheimer ◽  
Saul Wolfe

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.



1979 ◽  
Vol 32 (10) ◽  
pp. 2147 ◽  
Author(s):  
PA Corrigan ◽  
RS Dickson

Six organometallic complexes have been isolated from the reaction between (η-C5H5)Ir(C0)2 and hexafluorobut-2-yne at 120-160�. Both the cis and trans isomers of the σ-bridging alkyne complex (η C5H5)2Ir2(CO)2(CF3C2CF3) were obtained; the cis isomer is slowly transformed to the trans isomer at 160�. These complexes do not react further with alkynes. Two other products were identified as an iridiocyclobutenone complex and a iridiocyclopentadiene complex, viz.(η-C5H5){IrC(CF3)=C(CF3)CO}(CO) and (η-C5H5){IrC(CF3)=C(CF3)C(CF3)}(CO)These complexes are also inert to further reaction with hexafluorobut-2-yne, and the iridiocyclopentadiene complex could not be converted into the cyclopentadienone complex (η-C5H5)Ir{C4(CF3)4-CO). The spectroscopic properties of a product of formula (η-C5H5)Ir(CF3C2CF3)2(C4HF5) indicate it incorporates a 1-(2',2'-difluoroethenyl)-1,2,3,4,5-pentakis(trifluoromethyl)cyclopenta-2,4-diene ligand. The final product was formulated as (η-C5H5)Ir2(CO)3(CF3C2CF3)2H and five alternativestructures are consistent with the spectroscopic data. The related reaction between (η-C5H5)Ir(CO)2 and but-2-yne at 180� gives a small amount of hexamethylbenzene plus the maleoyl complex(η-C5H5){IrC(O)(Me=C(Me)C(O)}(CO).



1995 ◽  
Vol 48 (4) ◽  
pp. 879 ◽  
Author(s):  
PSK Chia ◽  
AJ Leong ◽  
LF Lindoy ◽  
GW Walker

Carrier-mediated transport of the cis and trans diastereoisomers of the diamminebis (ethane-1,2-diamine)cobalt(III) cation across a chloroform membrane by the natural ionophore lasalocid A is reported. In the case where individual isomers were run, no significant difference in their transport behaviour was observed. However, a competitive transport experiment in which equimolar concentrations of the cis and trans isomers of the above cation were present in the source phase led to enhanced transport of the trans isomer relative to the cis. Under the conditions employed, the final cis-to-trans ratio in the receiving phase was 1 : 3.



2007 ◽  
pp. 3966 ◽  
Author(s):  
Karel D. Klika ◽  
Henri Kivelä ◽  
Vladimir V. Ovcharenko ◽  
Ville Nieminen ◽  
Reijo Sillanpää ◽  
...  




1964 ◽  
Vol 47 (5) ◽  
pp. 838-841
Author(s):  
Morton Beroza ◽  
Rafael Sarmiento

Abstract Means of analyzing trimedlure, medlure, siglure, butyl sorbate, cue-lure, and methyleugenol by gas chromatography have been devised to ensure the procurement of high quality attractants needed for the detection of insect pests, especially those invading noninfested areas. The methods permit the estimation of the 4 trans isomers present in commercially produced trimedlure and medlure, and of the cis and trans isomers of siglure. Commercially available butyl sorbate gives a single sharp peak and is supposed to be the trans, trans isomer. Cue-lure and methyleugenol each give a single peak.



1993 ◽  
Vol 47 (4) ◽  
pp. 475-478 ◽  
Author(s):  
S. Chadha ◽  
W. H. Nelson ◽  
R. Emrich ◽  
E. Lindesmith

The Raman spectra of cis, trans, and vinyl isomers of crotyl chloride (i.e., cis and trans 1-chloro-2-butene, and 3-chloro-1-butene) have been excited at 218 nm and at 231 nm. With 218-nm excitation the ethylenic mode belonging to the vinyl isomer is only modestly preresonance enhanced. On the other hand, the preresonance enhancement of the peaks belonging to the cis and trans isomers is very noticeable and nearly identical in energy to the peaks of cis and trans polybutadiene, which occur at 1655 and 1665 cm−1, respectively. However, with 231-nm excitation the vinyl-isomer ethylenic mode at 1633 cm−1 is very strongly enhanced, while the cis and trans isomer modes show no corresponding enhancement, but appear to decrease in relative intensity. Responsibility for the strong vinyl group enhancement is assigned to an electronic transition observed as a broad shoulder near 230 nm. By exciting at 231 nm it is possible to detect small amounts of the vinyl isomer in the presence of cis and trans crotyl chloride. Remarkably strong enhancement under 231-nm excitation has been noted as well for the first overtone of the vinyl ethylenic mode observed at 3263 cm−1.



1965 ◽  
Vol 43 (5) ◽  
pp. 1345-1356 ◽  
Author(s):  
J. L. R. Williams ◽  
J. M. Carlson ◽  
R. E. Adel ◽  
G. A. Reynolds

The photochemical behavior of 4′-amino-, 4′-dimethylamino-, 4′-diethylamino-, and 4′-di-n-propylamino-substituted trans-2-styrylpyridine were studied. Ultraviolet irradiation of aqueous solutions of the bishydrochlorides and methiodide–hydrochlorides for moderate periods of time produced mixtures of the corresponding cis and trans isomers. Long irradiation times produced the corresponding dimers in all cases except that of trans-4′-di-n-propyl-amino-2-styrylpyridine. The cis isomers of the free bases and methiodides were isolated from the cis–trans mixtures. The trans-methiodides are not photochemically labile. The spectra of each pair of isomers were determined in water and in 50% methanol–water, with the exception of the 4′-di-n-propylamino derivative, which is not sufficiently water soluble. In addition, the spectra of the corresponding methiodides, hydrochlorides, bishydrochlorides, and methiodide–hydrochlorides were determined. The basic strengths of the nitrogens in the cis–trans isomer pairs of the free bases and methiodides have been determined spectroscopically in water and in 50% methanol-water.



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