Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt
Introduction
For more than 60 years, phosphonium derivatives has been extensively investigated in organic synthesis, especially in constructing CC double bonds. These types of compounds have been widely used as reactants in the Wittig olefination reaction of carbonyl compounds (aldehydes, ketones, lactones, etc.) [1], [2], [3], [4]. Much investigation concerning ylide compounds have been conducted by experimental and theoretical chemists. In between studies, oxidation is an important preparation process in the phosphonium ylide chemistry, which can be performed with a lot of oxidizing agents [5], [6], [7], [8], [9], [10], [11], [12], [13], [14]. Wasserman et al. applied the sequence of reactions (acylation, oxidation, aminolysis) to the α-cyanomethyl phosphonium ylide in order to synthesize various peptidic biological active compounds [5], [6], [7], [10]. Moreover, the groups of Kawamura [12] and Lee [13], [14] synthesized 1,2,3-tricarbonyl compounds by oxidation of disubstituted stabilized ylides. The preparation of all-(Z)-cyclododecatetraene by oxidation of the appropriate bis-ylide is also reported in recent years [15].
On the other hand, bisphosphine monoxides are also known as an important class of phosphorus ligands containing both soft (P) and hard (O) donor centers [16], [17], [18], [19]. However, the synthesis of entitle ligands, and the study of their complexation to transition metals, is a less documented field; in spite of their practical importance. These compounds can be used as ligand incoordination chemistry and catalyst in chemistry reactions [20], [21], [22], [23], [24], [25], [26], [27]. The reaction of 1,2-bis(diphenylphosphino)ethane monoxide (dppeO) with various mercury(II) halides reported in 2007 by Ebrahim et al. [25]. However, in the present work we have found quite different patterns of reactivity of similar ligand toward mercury(II) halides. With the aim to expand this research theme, we have studied the reactivity of the new phosphonium-phosphine oxide salt [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]Br (1) toward mercury(II) iodide. Herein, the synthesis, spectral and structural characterization of this ligand (1) and its mercury(II) iodide complex (2) are reported.
Section snippets
Materials and physical measurements
The chemicals and solvents used in this work are of analytical grade and available commercially and were used without further purification. NMR spectra were acquired on a 300 MHz Bruker spectrometer in CDCl3 and DMSO-d6 with TMS as the internal standard. All chemical shift values were recorded in ppm (δ). Coupling constants are given in Hz. IR spectra were recorded on a FT BOMEM MB102 spectrophotometer and the measurements were made by the KBr disk method. Elemental analyses (C, H, N) were
Synthesis and general characterization
The preparation of the phosphonium-phosphine oxide salt (1) was carried out by reaction of the diphosphine (dppe) with 4-nitrophenacyl bromide. The 31P NMR and IR of the compound 1 give some evidence for the formation of the phosphonium-phosphine monoxide salt. Recently, we have reported the synthesis of corresponding phosphonium-phosphine salt using a similar reaction under dry nitrogen atmospheres [28]. The IR spectra of the compound 1 shows strong bands at 1191and 1684 cm−1, attributed to
Conclusion
The reactions of the mercury(II) halide with new synthesized phosphonium-phosphine oxide salt revealed different product as a result of their various tendencies toward the halide ions. Formations of the latter complex have been confirmed by spectroscopic and crystallography techniques. The crystal structure consists of phosphonium-phosphine oxide cations, [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2+, and dimermercurat(II) anions, [Hg2I5Br]2−. Interestingly, the phosphine oxide expressed its tendency
Acknowledgements
We thank Shahid Chamran University of Ahvaz (Grant Number: 1395) for financial support.
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