From neutral iminophosphoranes to multianionic phosphazenates. The coordination chemistry of imino–aza-P(V) ligands

Synthesis, Structure, Reactivity, and Catalytic Activity of C,N‐ and C,N,N‐Orthopalladated Iminophosphoranes

“…The reaction of Pd(OAc) 2 (OAc = acetate) with Ph 3 P=NPh (1:1 molar ratio) in refluxing CH 2 Cl 2 , followed by evaporation to dryness and treatment of the residue with excess LiCl in MeOH, gives the orthometallated dimer [Pd(C 6 H 4 -2-PPh 2 =NPh-κ-C,N)(μ-Cl)] 2 (1) in very good yield (see Scheme 1). It has been previously reported that complexes related to 1, but with different aryl substituents, can be obtained from the reaction of Na 2 [PdCl 4 ] [36] or Pd(OAc) 2 [37] and the corresponding iminophosphoranes in moderate to good yields (56-97 %). The synthesis of 1 has been reported very recently [38] from the reaction of [o-C 6 H 4 -PPh 2 NPh)Li] 2 ·OEt 2 with [PdCl 2 (COD)] (COD = 1,5-cyclooctadiene).…”

“…the aza-Wittig reaction), either as neutral or as anionic reagents. [1][2][3] In addition, the bonding properties of these compounds as ligands towards transition metals are still attracting the interest of chemists, for several reasons: their ability to form and to stabilize carbene complexes, [5,8] the easy modulation of the electronic and steric properties of different types of catalysts (for instance, in oligo-and polymerisation of ethylene, [4,6,23] hydrogen-transfer processes, [9,10] etc. ), their applications in enantioselective synthesis and catalysis (allylic substitution), [25,26] the synthesis of alkaline earth organometallic complexes, [7] and, in general, due to their versatility.…”

Tris(organozinc) Phosphazenates as Templates for Trimeric and Hexameric Zinc Oxide Clusters

“…[4] Over the past years, we have studied the coordination behavior of multianionic phosphazenate ligands. [5] The trianionic ligand A features three anionic N centers at equatorial positions (N eq ) of the chair-shaped {P 3 N 3 } ring and offers three chelating N eq -N ring sites (Scheme 1). [6] Herein, we report that the tris(ethylzinc) complex B can act as a template for trimeric and hexameric zinc oxide clusters through the bowlshaped coordination surface of three Lewis basic N eq functions and three Lewis acidic Zn centers.…”

The Cα‐Deprotonated Iminophosphorane Ph2P(CH2Py)(NSiMe3) as an N,N‐Chelating Ligand for Iron and Zinc

“…[7] Additionally, P-alkyl-substituted iminophosphoranes can easily be deprotonated to give attractive building blocks for metallacycles. [8] The introduction of alkyl bridges between the phosphorus atom and the donating heterocycle in the ligand periphery of iminophosphoranes provides not only the opportunity of a higher geometrical adaptability by a wider bite but can also allow the formation of anionic species. Delocalisation of the carbanionic charge to the donating atoms would enable the ligand to respond to the various requirements of metal atoms with their different radii and polarisability.…”