Molecular structure of the carbon-bound phosphorus ylide complex trans-dichlorobis(benzoyltri-n-butylphosphorane)palladium(II)

Synthesis of a new carbbenzyloxymethylenetriparatolylphosphorane ylide and study of its reaction with mercury(II) halides: Spectral and structural characterization

“…This indicates probably, that the ylide dissociate in solution. Compounds wherein the ylide is C-coordinated exhibit a 2 J(PH) value 10 or less Hz [12,8,33].…”

“…This so-called a-stabilization provides BTPY with the potential to act as an ambidentate ligand and thus bond to an Hg(II) centre through the either carbanion (b) or the enolate oxygen (c). Although many bonding modes are possible for keto ylides [8], coordination through carbon is more predominant and observed with soft metal ions, e.g., Pd(II), Pt(II), Ag(I), Hg(II), Au(I) and Au(III) [9][10][11][12][13], whereas, O-coordination dominates when the metals involved are hard, e.g., Ti(IV), Zr(IV), and Hf(IV) [14]. In this work we have synthesized benzyloxy stabilized phosphorus ylide and metal complexes with mercury(II) halides.…”

Synthesis and characterization of new nitrate-bridged polymeric complexes of mercury(II) with phosphorus ylides

“…The 31 P NMR spectra at room temperature clearly exhibit the previously mentioned satellites (8% intensity each, 2 J PHg $295 Hz) while these satellites for ylidic complexes of Hg(II) halides are only observed at low temperature [5,19,20,22] or by solid state 31 P NMR [22]. Variable temperature 31 P NMR study on 2d, using DMSO-d 6 as solvent showed that disappearance of satellites occurs when the a: X = Cl, Ar = C 6 H 5 b: X = Cl, Ar = C 6 H 4 -CH 3 c: X = NO 2 , Ar = C 6 temperature is increased to 65°C (Fig. 1).…”

“…The significance of the Hg-C bond length, 2.134(4) Å in 2a compared to analogous distances in [BPPY AE HgI 2 ] 2 [6] and in [(C 6 H 5 ) 3 -PC 5 H 4 AE HgI 2 ] 2 [31] (2.312(13) and 2.292(8) Å , respectively) must be attributed to the use of Hg(II) orbitals with high s character for bonding to ylidic carbon. As expected on the basis of the Bent rule, the Hg-C bonds in 2a and [BPPY AE HgCl 2 ] 2 [6] are much shorter than in [BPPY AE HgI 2 ] 2 because of the very low difference in electronegativity between carbon and iodine.…”

“…This so-called a-stabilization provides ylides with the potential to act as an ambidentate ligand and thus bond to an Hg(II) centre through the either carbon (B) or oxygen (A 1 and A 2 ) (Scheme 1). Although many bonding modes are possible for keto ylides, [6] coordination through carbon is more predominant and observed with soft metal ions, e.g., Pd(II), Pt(II), Ag(I), Hg(II), Au(I) and Au(III), [5,[7][8][9][10] whereas, O-coordination dominates when the metals involved are hard, e.g., Ti(IV), Zr(IV), and Hf(IV) [11].…”