Synthesis of New Phosphonium Ylides Containing Thiophene and Furan Rings and Study of Their Reaction with Mercury(II) Halides: Spectral and Structural Characterization

Abstract

¼ Cl, Br, and I) in equimolar ratios in MeOH as solvent leads to the binuclear products 1 -3 (Scheme 1). The bridgesplitting reaction of the binuclear complex [{HgI 2 (bbtppy)} 2 ] (3c) by DMSO yields the mononuclear complex [HgI 2 · (bbtppy) (DMSO)] (3d) (Scheme 2). This bridge-splitting reaction can also be a method for the synthesis of mononuclear products. C-Coordination of the ylide and O-coordination of DMSO are demonstrated by a single-crystal X-ray-analysis of the mononuclear complex 3d. Characterization of the obtained compounds was also performed by means of elemental analysis and IR and 1 H-, 31 P-, and 13 C-NMR spectroscopy. A theoretical study of some Hg II complexes with phosphonium ylides is also reported.Introduction. -The coordination chemistry of the phosphonium ylides (¼ phosphoranes) of the type R 3 P þ ÀCH 2 À , is well known [1 -4]. Resonance-stabilized phosphonium ylides, particularly, the keto ylides, are also successfully used as ligands in organometallic and coordination chemistry owing to their accessibility and stability towards air and moisture [5] [6]. Juxtaposition of the keto group and the carbanion in the phosphonium ylides allows for the resonance delocalization of the ylide electron density providing additional stabilization to the ylide species. This so-called astabilization provides ylides with the potential to act as an ambidentate ligand and thus bond to an Hg II center through either the C-atom (see B) or O-atom (see A 1 and A 2 ). Although many bonding modes are possible for keto ylides [7], coordination through the C-atom is more predominant and observed with soft metal ions, e.g., Pd II , Pt II , Ag I , Hg II , Au I , and Au III [8] [9 -12], whereas O-coordination dominates when the metals involved are hard, e.g., Ti IV , Zr IV , and Hf IV [13].

catena-Poly[[chlorido[1-(3-nitrophenyl)-2-(triphenylphosphoranylidene)ethanone-κC2]mercury(II)]-μ-chlorido]

“…The latter distance being rather long, indicates a weak Hg-Cl(bridging) interaction. The Hg-C bond length in the title compound, 2.244 (3) Å, is consistent with values reported for mono ([HgI 2 (bbtppy)(DMSO)]) and dimeric ([(bappy)HgI 2 ] 2 ) Hg II -C complexes (Sabounchei et al, 2007(Sabounchei et al, , 2008(Sabounchei et al, , 2009(Sabounchei et al, , 2011Sabounchei, Jodaian et al, 2010;. In the crystal structure, adjacent polymer chains interact via C-H…”

“…For an example of a one-dimensional polymeric Hg II complex, see: Ebrahim et al (2007). For mono-and dimeric complexes of Hg II containing ylide ligands, see: Sabounchei et al (2007Sabounchei et al ( , 2008Sabounchei et al ( , 2009Sabounchei et al ( , 2011; Sabounchei, Jodaian et al (2010); . Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.…”

A series of nanoscaled Pt(0)‐phosphorus ylide complexes based on [60]fullerene: Synthesis, characterization, and in vitro biological assessments

“…It must be also noted that O‐coordination leads to a different set of signals in all NMR spectra. [ 24 ] Figure 1 shows how to recognize the structure of synthesized nanocomplexes Pt(0)‐C 60 by IR and NMR spectroscopic analyses.…”

New Pd‐phosphorus ylide complexes based on FC60 as heterogeneous nano‐catalyst for H/D exchange reaction

“…It must be noted that the O-coordination of the ylide generally leads to the formation of cisoid and transoid isomers, giving rise to two different sets of signals in all NMR spectra. [21] Table 1 summarizes the IR and NMR spectral data for complexes 1-4 and related phosphorus ylides.…”