Chapter 8. Analytical reagents having oxygen (O) as donor atom

Palladium(II) ammine complexes enriched in 15N give sharp singlets in their 15N n.m.r . spectra. The 15N chemical shifts depend primarily on the trans donor atom, in a qualitatively similar way to those for platinum(II) ammine complexes. A dimethylformamide solution of Pd(NH3)2Cl2 prepared in the usual way gave a single peak, consistent with the presence of only one isomer (trans). Reactions of increasing amounts of aqueous perchloric acid with Pd(NH3)42+ allowed peaks to be identified for Pd(NH3)3(H2O)2+, cis -Pd(NH3)2(H2O)22+ and Pd(NH3)(H2O)32+. The initial product of the reaction of trans-Pd(NH3)2Cl2 with silver ion is trans-Pd(NH3)2(H2O)22+, which rapidly disproportionates to Pd(NH3)3(H2O)2+ and Pd(NH3)(H2O)32+. With standing, subsequent reactions ultimately produce a solution containing predominantly cis -Pd(NH3)2(H2O)22+ in equilibrium with small amounts of the tri- and mono-ammine complexes, and free ammonia.

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Stereochemistry of Cobalt(III) Complexes with Thioethers. III. Vicinal Circular Dichroism due to the Chiral Sulfur Donor Atom

Bulletin of the Chemical Society of Japan ◽

10.1246/bcsj.50.2451 ◽

1977 ◽

Vol 50 (9) ◽

pp. 2451-2458 ◽

Cited By ~ 14

Author(s):

Kazuaki Yamanari ◽

Jinsai Hidaka ◽

Yoichi Shimura

Keyword(s):

Circular Dichroism ◽

Donor Atom ◽

Circular Dichroïsm ◽

Sulfur Donor

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N-ACYL SUBSTITUTED PHENYLHYDROXYLAMINES: THE EFFECT OF RADICAL CHANGE ON ANALYTICAL BEHAVIOR

Canadian Journal of Chemistry ◽

10.1139/v57-192 ◽

1957 ◽

Vol 35 (12) ◽

pp. 1454-1460 ◽

Cited By ~ 18

Author(s):

C. A. Armour ◽

D. E. Ryan

Keyword(s):

Aqueous Solution ◽

Stability Constant ◽

Radical Change ◽

Spectrophotometric Study ◽

Iron Complex ◽

Membered Ring ◽

Analytical Reagents ◽

Colorimetric Reagent ◽

Analytical Behavior

The synthesis of a number of N-acyl substituted phenylhydroxylamines is outlined and the effect of the change in the nature of the acyl group on their usefulness as analytical reagents is described. Stability constant measurements in alcohol show an increase in stability with an increase in basicity of reagent regardless of the nature of the attached group; their ability to precipitate complexes from aqueous solution, however, is markedly dependent on the nature of the attached radical. A spectrophotometric study shows the existence of both a 1:1 and a 1:3 iron complex. A more sensitive colorimetric reagent results with an unsaturated five-membered ring as the attached grouping.

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