Bonding properties and bond activation of ylides: recent findings and outlook

Abstract

The interaction of phosphorus and nitrogen ylides with metallic precursors has been examined from different points of view. The first one is related to the bonding properties of the ylides. Ylides with a unique stabilizing group bond through different atoms (the Calpha or the heteroatoms); while ylides with two stabilizing groups never coordinate through the Calpha atom. In the second section we examine the cause of the stereoselective coordination of bisylides of phosphorus, nitrogen and arsenic, and of mixed bisylides. We describe here the very interesting conformational preferences found in these systems, which have been determined and characterized. The DFT study of these bisylides has allowed for the characterization of strong intramolecular PO and AsO interactions, as well as moderate CHO[double bond, length as m-dash]C hydrogen bonds as the source of these conformational preferences. The third topic is related to the amazing reactivity of phosphorus ylides in bond activation processes. Depending on the nature of the metallic precursors, ylides can behave as sources of carbenes, of phosphine derivatives, of other ylides or of orthometallated complexes through P[double bond, length as m-dash]C, P-C or C-H bond activation reactions.

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

“…It is interesting to note that, in addition to the major resonances discussed above, the 31 P NMR spectra in CDCl 3 show the presence of two other minor species. One set of two doublets in the region of 26.06 ppm and 21.75 ppm in the 31 P NMR spectra can be attributed to [O@PPh 2 CH 2 P + Ph 2 CH 2 COPh]X À (where X = anion concerned).…”

“…Much of the interest in the coordination properties of resonance stabilized phosphorus ylides stems from their ligating versatility due to the presence of different functional groups in their molecular skeleton [3]. The monoketo ylides derived from bisphosphines, viz., Ph 2 PCH 2 PPh 2 @C(H)C(O)R, Ph 2 PCH 2 CH 2 PPh 2 @ C(H)C(O)R (R = Me, Ph or OMe) [4] contain a P donor site in addition to C donor (the ylidic C) or O donor (the carbonyl O) sites for coordination, and therefore can engage in different kinds of bonding with metal ions.…”

Synthesis, characterization, crystal structure, theoretical studies, and antibacterial activities of P-coordinated mercury(II) complexes containing phosphine–phosphonium salts

“…The phosphonium salts are most often converted to phosphorus ylides by releasing a proton. The efficiency of metalated phosphorus ylides in synthetic chemistry has been well documented [19][20][21][22][23][24][25][26][27]. Most of the interest in the coordination properties of resonance stabilized phosphorus ylides stemming from their bond versatility is due to the presence of different functional groups in their molecular structure [20].…”

Synthesis, characterization and theoretical and fluorescence emission microscopy studies of new Pd/Pt–cyclopropa[60]fullerene complexes: Application of Taguchi method for optimization of parameters in Suzuki–Miyaura reaction

“…Experimental and theoretical studies of the reactivity and coordination chemistry of carbonyl‐stabilized phosphorus ylides are an important research field of our group . Because of various coordination modes of α‐keto‐stabilized phosphorus ylides in metal complexes (P‐, C‐ and P,C‐coordination modes), these compounds are attractive candidates for further development in Pd/Pt–cyclopropa[60]fullerene complexes …”