Triphenylphosphine complexes of mercury(II) acetate and fluoroacetates. Preparation, characterization, and spectral studies
- 1 January 1979
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 57 (1) , 91-97
- https://doi.org/10.1139/v79-015
Abstract
Triphenylphosphine reacts with mercury(II) acetate and fluoroacetates to form complexes of the types Ph3PHg(O2CR)2, (Ph3P)2Hg(O2CR)2, and (Ph3P)3Hg(O2CR)2, where R = CH3, CH2F, CHF2, or CF3. The 1:1 and 2:1 have been isolated and characterized by elemental analysis, molecular weight, and conductance measurements and by vibrational and nmr spectroscopic studies. The formation of the 3:1 complexes is inferred by 31P nmr spectral measurements at 183 K. Both the 1:1 and 2:1 complexes are indicated to be monomeric molecular species in which the O2CR groups are bidentately bonded to mercury. The Hg—O and Hg—P stretching frequencies for these complexes have been assigned by infrared and Raman spectral measurements. The 199Hg–31P spin–spin coupling constants and the 31P coordination chemical shifts for the 1:1 as well as the 2:1 complexes increase in the order: O2CCH3 < O2CCH2F < O2CCHF2 < OCCF3 Correlations between 1J(199Hg–31P) values, 31P coordination chemical shifts, and the pKa values for the carboxylic acids are discussed.Keywords
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