Mercury-Amine Complexes and Aromatic Mercurials: a Study of Compounds Containing Mercury-Nitrogen and Mercury-Carbon Bonds in Aqueous Solution

Author: Wirth, Thomas Henry

Year: 1964

Degree: Dissertation (Ph.D.)

Advisor: Davidson, Norman R.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/2P2A-GE19

Abstract

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The Hg(II) complexes of aniline, guanidine, and ammonia have been studied potentiometrically in aqueous solution with a mercury electrode. The stability of the HgR[subscript 2][superscript ++] complexes of these compounds correlates well with their basicities. An RHgOH[superscript +] complex (R = guanidine) has been identified potentiometrically and its stability determined.

Potentiometric evidence for the existence of a 1: 1 Hg(I)-aniline complex was confirmed spectrophotometrically. The complex is less stable than the corresponding complex of Hg(II). No 2: 1 complex (Hg[subscript 2] L[subscript 2][superscript ++]) was observed.

The 1: 1 complexes of aniline and para-mercurated aniline with Hg(II) were studied spectrophotometrically. Cationic, ring mercurated anilines bind Hg(II) strongly; no decrease in complex stability occurs as -Hg[superscript +] groups are added to the aromatic ring. Complexes of Hg(II) with mercurated anilines exhibit a unique ultraviolet absorption band at 330-335 m[mu] in aqueous solution.

Slow but pronounced spectral changes occur in aqueous Hg(C1O[subscript 4])[subscript2]-HC1O[subscript 4] solutions containing small amounts of [psi]NH[subscript 3C1O[subscript 4] which are allowed to stand. These changes have been interpreted in terms of mercuration of the aniline and the formation of Hg(II) complexes with the products.

Single crystals of an explosive Hg(II)-aniline compound C[subscript 6]NH[subscript 3]Hg[subscript 3](C1O[subscript 4)[subscript 2] [...] 4H[subscript 2]O have been prepared.

Equilibrium in the mercuration of benzene and p-methoxy anisole has been studied at room temperature in aqueous HC1O[subscript 4]NaC1O[subscript 4] solution in the presence of excess organic. An analytical procedure utilizing the U.V. absorption of the HgC1[subscript 4][superscript =] complex was used. The equilibrium quotient of the reaction C[subscript 6]H[subscript 6] + Hg[superscript ++] = C[subscript 6H[subscript 5]Hg[superscript +] +H [superscript +] lies in the range 70-500.

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