Elsevier

Journal of Molecular Structure

Volume 1129, 5 February 2017, Pages 319-324
Journal of Molecular Structure

Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt

https://doi.org/10.1016/j.molstruc.2016.09.079Get rights and content

Abstract

The reaction of new phosphonium-phosphine oxide salt [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]Br (1) with mercury(II) iodide in a methanolic solution yielded [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2[Hg2I5Br](2). These two compounds were fully characterized by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. Crystal and molecular structure of 2 has been determined by means of X-ray diffraction. In mercury compound, the phosphine oxide salt is found as a counter ion letting the mercury(II) ion to bound halides to all four coordination sites and to give dimermercurate(II) ions as the structure-constructing species. The neighboring [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2+cations are joined together by intramolecular Csingle bondH⋯O hydrogen bonds to give a 1-D chain structure along the crystallographic b-axis. The [Hg2I5Br]2−anions act as cross-linkers between neighbouring strands extending the supramolecular structure into 2D layers in (110) planes as well as balances the charge of the complex. The significant effects of Csingle bondH⋯X (Xdouble bondO, Br and I) and π⋯π aromatic interactions play a major role in the crystal packing of compound 2.

Introduction

For more than 60 years, phosphonium derivatives has been extensively investigated in organic synthesis, especially in constructing Cdouble bondC 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.

References (40)

  • H.H. Wasserman et al.

    Tetrahedron Lett.

    (1997)
  • H.H. Wasserman et al.

    Tetrahedron Lett.

    (2000)
  • K. Lee et al.

    Tetrahedron Lett.

    (2001)
  • M.M. Ebrahim et al.

    Polyhedron

    (2007)
  • S. Samiee et al.

    Polyhedron

    (2015)
  • V. Nobakht et al.

    Inorg. Chim. Acta

    (2014)
  • S.J. Sabounchei et al.

    J. Organomet. Chem.

    (2008)
  • N.A. Bell et al.

    Inorg. Chim. Acta

    (1983)
  • A. Lledós et al.

    Inorg. Chem.

    (2004)
  • G. Wittig

    Angew. Chem.

    (1980)
  • B.E. Maryanoff et al.

    Chem. Rev.

    (1989)
  • O.I. Kolodiazhnyi

    Russ. Chem. Rev.

    (1997)
  • G. Hilt et al.

    J. Org. Chem.

    (2007)
  • H.H. Wasserman et al.

    J. Org. Chem.

    (1997)
  • H.H. Wasserman et al.

    J. Org. Chem.

    (1994)
  • H.H. Wasserman et al.

    J. Am. Chem. Soc.

    (1999)
  • H.H. Wasserman et al.

    Helv. Chim. Acta

    (2000)
  • O.I. Kolodiazhnyi

    Phosphorus Ylides: Chemistry and Application in Organic Synthesis

    (1999)
  • Y. Kawamura et al.

    Phosphorus Sulfur Silicon

    (1999)
  • K. Lee et al.

    Bull. Korean Chem. Soc.

    (2000)
  • Cited by (4)

    • A new and unexpected coordination mode of a bis-phosphine monoxide (BPMO) ligand in a palladacycle complex

      2022, Journal of Molecular Structure
      Citation Excerpt :

      This coupling constant (2JP–P) are found about 50 Hz, which is in good agreement with biphosphine ligands[42–45]. The 1H NMR spectrum showedall protons in the expected regions and was analogous with the spectra of the corresponding bis-phosphine ligand (1) [42–45]. Due to the coupling of methylene and methine protons with the neighboring phosphorus atoms, the signals for the PCH2 and PCH groups appeared as two broad resonances at 3.52 and 4.70 ppm, respectively.

    • Synthesis, crystallographic studies, antibacterial and antifungal activities of mononuclear mercury(II) complexes derived from [PPh<inf>2</inf>(CH<inf>2</inf>)<inf>n</inf>PPh<inf>2</inf>CH<inf>2</inf>C(O)C<inf>6</inf>H<inf>4</inf>Cl)]Br ligands

      2020, Polyhedron
      Citation Excerpt :

      However, some metal complexes are among the most widely used antibacterials, but assessment of antibacterial activity of new metal complexes with ligands system is very necessary. Herein, in continuation of our previous reports [39,40], we are interested to investigate the reactivity of two ligands derived from dppm and dppe (S1 and S2) with mercury(II) halides which can be composed (i) zwitterionic complexes containing P-coordination mode or (ii) ylide complexes by deprotonation or (iii) phosphonium metalates where the metal remains uncoordinated to the ligand. In addition, the antibacterial and antifungal activities of the synthesized ligands and their complexes reported.

    • Phosphonium salts derived from Α-ferrocenylvinyl cation in situ generated in sc-CO<inf>2</inf> from ethynylferrocene by Nafion film

      2018, Journal of Supercritical Fluids
      Citation Excerpt :

      The C (1) −C (11) 1.515 (3) Å and C (11) −C (12) 1.548 (3) Å bond lengths coincide with standard values of ordinary Csp2Csp3 and Csp3Csp3 bond lengths (1.51 and 1.54 Å [58]), respectively. The six-membered cycle is in chair conformation that is similar to that one found for relative moieties, C-unsubstituted tetraphenyl-P2C4 [59] and tetracyclohexyl-P2C4 [60] cycles. On purification by preparative TLC on Al2O3, salt 4 was found to undergo it a hydrolytic scission of the P-C(Fc) bond giving rise (ferrocenylvinyl)phosphonium phosphine oxide tetrafluoroborate 5.

    • Phosphine chalcogenides

      2019, RSC Catalysis Series
    View full text