Reactivity of mercury(II) halides with the unsymmetrical phosphorus ylide Ph2PCH2CH2PPh2C(H)C(O)Ph: Crystal structure of {HgI2[PPh2CH2CH2PPh2C(H)C(O)Ph]}n

Abstract

The unsymmetrical phosphorus ylide, Ph 2 PCH 2 CH 2 PPh 2 @C(H)C(O)Ph is shown to react with Hg(II) halides to form polymeric products with the composition {HgX 2 [PPh 2 CH 2 CH 2 PPh 2 C(H)C(O)Ph]} n , where X = Cl (1), Br (2), I (3). The complexes have been characterized by elemental analysis, IR, 1 H, 31 P NMR spectra as well as by ESI mass spectra. In product 1 the ylide exhibits a P, C-bridging mode of coordination, while in 2 and 3 it shows a monodentate P-coordination with the dangling ylide. The structure of complex 3 has been characterized crystallographically. The monomeric -Hg-I-Hg-bridging in 3 leads to a zig-zag polymeric chain in which mercury assumes a distorted tetrahedral geometry.

Four-coordinate Pd(II) complexes containing non-symmetric phosphorus ylides: Synthesis, characterization, and catalytic behavior towards Suzuki reaction

“…The PeC, coordinated mode had been previously observed for Pd(II), Pt(II), Rh(I), Hg(II) [3e12]. In addition, Rh(I) and Hg(II) were shown to exhibit the P-bonding mode [5,12]. In this work, we have now focused our attention in the study of the coordination mode adopted by the resonance stabilized ylides when ligated to Pd(II).…”

“…Coordination of the ylides through C-coordination causes an increase in n(CO) [41e43] while for O-coordination a lowering of n(CO) is expected [44]. Thus, the IR data obtained indicates that the interaction of the ligands with palladium(II) chloride are through the ylidic carbon atom and PPh 2 group [5,45], as proved by the crystal structure of 1 (vide infra).…”

Four-coordinate and pseudo five-coordinate Hg(II) complexes of a new bidentate phosphorus ylide: X-ray crystal structure and spectral characterization

“…The a-keto stabilized ylides derived from bisphosphines, viz., Ph 2 PCH 2 PPh 2 @C(H)C(O)R, Ph 2 P-(CH 2 ) 2 PPh 2 @C(H)C(O)R (R = Me, Ph or OMe) [6] and PhC(O)C(H)@ PPh 2 CH 2 CH 2 PPh 2 @C(H)C(O)Ph [7] form an important class of hybrid ligands containing both phosphine and ylide functionalities, and can exist in ylidic and enolate forms. These ligands can therefore engage in different kinds of bonding with metal ions [6][7][8][9][10][11][12][13][14][15][16][17].…”

Mercury(II) complexes of stabilized phosphine–phosphonium ylide derived from bis(diphenylphosphino)methane: Synthesis, spectra and crystal structures

“…However, HgBr 2 and HgI 2 react with the same ylide giving polymeric halogen bridged phosphine complexes with dangling ylide [10]. Such a versatile reactivity has prompted us to expand our studies to related mixed phosphine-phosphonium ylide with mercuric halides.…”