Group 11 Metal Complexes of the Mesocyclic Thioether Aminophosphonites [‐OC₁₀H₆(μ‐S)C₁₀H₆O‐]PNC₄H₈E (E = O, NMe)

Abstract

Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC 10 H 6 (µ-S)C 10 H 6 O-]PNC 4 H 8 E {2a: E = O; 2b: E = NMe; IUPAC names:

Large-bite bisphosphite, 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2: Synthesis, copper(I), and gold(I) complexes

“…Similar to the aminophosphonite and phosphonite ligands containing eight membered heterocycles reported by Punji et al, the ligand 3 contains two cyclic phosphite units in which because of P-S interaction the geometry around the phosphorus atoms displaces from pyramidal to a pseudotrigonal bipyramidal [6][7][8][9]. Very similar displacements were earlier observed, where varying degree of sulfur coordination to phosphorus resulted in structural displacements from square pyramidal to octahedral [11].…”

“…Both phosphorus and sulfur are excellent donor atoms for a wide range of transition metals, in particular group 11 metals, while the low ionization energy of sulfur and the existence of several lone pair of electrons (three in the case of a thiolate anion) offer the possibility of a rich sulfur based chemistry of the complexes [5]. Recently we have reported the syntheses of both large-bite and short-bite bisphosphonite ligands containing mesocyclic thioether functionalities and reported their reactivity towards platinum and group 11 metals where it exhibits interesting coordination behavior producing neutral, cationic and anionic complexes [6][7][8][9][10]. The Pd II , Rh I and Ru II complexes have shown excellent catalytic activities towards various cross coupling reactions (Suzuki-Miyaura, Mizoraki-Heck and amination reactions) and hydrogenation of olefins.…”

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

“…Die Kristallstrukturen der C 2 -symmetrischen Komplexe [Rh(cod)(Phosphoramidit) 2 ]BF 4 und [Rh(MonoPhos) 4 ]BF 4 [58] zeigen zweifelsfrei die genannten geometrischen Merkmale, [46,53] die auch bei Gold-koordinierten Phosphoramidit-Liganden auftraten, die cyclische Amine wie Morpholin und Methylpiperazin enthalten (Tabelle 1 Eintrag 5). [59] Die elektronischen Eigenschaften von Phosphorliganden lassen sich anhand ihres p-Akzeptor-und s-Donorvermögen charakterisieren. Durch Vergleichen ihrer Metall-CarbonylKomplexe können aus den Frequenzen der C-O-Streckschwingung Rückschlüsse auf die p-Akzeptoreigenschaften der Liganden gezogen werden.…”

Cyclodiphosphazane cis‐{(o‐MeOC6H4O)P(μ‐NtBu)}2 as a Bridging Bidentate Ligand: Synthesis, Structures of Heterometallic Complexes, and Halogen Exchange Between Rh–Cl and Cu–X (X = Br, I)

“…Such complexes can be of importance in homogeneous catalysis to promote Scheme 1. more than one type of catalysis and also for exploring the catalytic activity of multimetallic systems. [7] As a continuation of our work on transition metal chemistry of phosphorus-based ligands and their catalytic applications, [8] we describe in this article the synthesis and molecular structures of several heterometallic complexes of cyclodiphosphazanes.…”