Preparation, photo- and electrochemical studies of a homoleptic imine-phosphaalkene Cu(I) complex

Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes

“…The ligand-based reduction was confirmed by performing CV studies on ligands 1 and 2, which revealed reversible reduction events at −2.36 V (Figure S27b) and −2.13 V (Figure S27e), respectively, in line with the theoretically determined electron affinities, showing that 2 is easier to reduce (vide supra). Compared to a recently reported imine-phosphaalkene, which shows a reversible reduction event at −1.85 V, 34 ligands 1 and 2 are reduced at considerably more negative potentials. In contrast to diphenyl-substituted phosphaalkenes, the reduction of 1 and 2 is reversible.…”

“…Similarly, Ozawa and co-workers showed that using the related Mes*-substituted P,N,P-type ligand, twofold cyclization occurred to give the corresponding bis-phospholanyl RhCl-complex (Scheme (bottom right)) . C–H bond activation is a common deactivation pathway for Mes*-containing low-valent P-species. , Other P,N-type phosphaalkene ligands have been reported and include phosphaalkenes with pendant imine functions, , pyridine-bridged oxazoline phosphaalkenes, chiral alkyl-bridged phosphaalkenes, and OSiMe 3 -substituted phosphaalkenes in a pyridine-bridged P,N,P-bisphosphaalkene . We have recently presented the convenient and large-scale synthesis of phospha-Wittig reagents, R–P­(PMe 3 ) with R = Mes*, Mes Ter and Dip Ter ( Dip Ter = 2,6-(2,6- i Pr 2 C 6 H 3 )-C 6 H 3 ) and showed that PMe 3 can be displaced by NHCs or NHOs, and furthermore serve as an interesting phosphinidene synthon for a variety of applications. , In the present study, these compounds are applied for the synthesis of a new π extended P,N-phosphaalkene ligand.…”

“…31 C−H bond activation is a common deactivation pathway for Mes*containing low-valent P-species. 32,33 Other P,N-type phosphaalkene ligands have been reported and include phosphaalkenes with pendant imine functions, 34,35 pyridine-bridged oxazoline phosphaalkenes, 36 chiral alkyl-bridged phosphaalkenes, 37 and OSiMe 3 -substituted phosphaalkenes in a pyridinebridged P,N,P-bisphosphaalkene. 38 We have recently presented the convenient and large-scale synthesis of phospha-Wittig reagents, R−P(PMe 3 ) with R = Mes*, Mes Ter and Dip Ter ( Dip Ter = 2,6-(2,6-iPr 2 C 6 H 3 )-C 6 H 3 ) and showed that PMe 3 can be displaced by NHCs or NHOs, 39 and furthermore serve as an interesting phosphinidene synthon for a variety of applications.…”

Core and double bond functionalisation of cyclopentadithiophene-phosphaalkenes

“…The cationic intermediate can be stabilised using 2,6-dimethylphenyl isocyanide 39 yielding the heteroleptic complex 10, which is characterised by a very broad 31 behaviour in solution and is commonly observed for phosphaalkene coinage metal complexes. 40,41 Interestingly, the deshielded β proton changes from 8.05 ppm in [AuCl•A] to 7.58 and 7.67 ppm in 10 and 11, respectively, illustrating the different electrostatic situations proximal to the Au(I) + centre, whereas the shielded β′ proton is barely influenced. The lowenergy absorption band in the UV/vis spectrum of the gold complexes is red-shifted by ca.…”

Organophosphorus Azoles Incorporating a Tetra-, Penta-, and Hexacoordinated Phosphorus Atom: NMR Spectroscopy and Quantum Chemistry

“…The Z-configuration of the compounds 1-4 is stable at room temperature, while upon heating, a partial Z-Е-isomerization occurs. The isomerization proceeds much more easily in passing from enaminotrichlorophosphonium hexachlorophosphates (1-4) to 2-(N-pyrazolyl)ethenylphosphonic acid chloroanhydrides (5)(6)(7)(8), and occurs during storage of phosphonic acid chloroanhydrides. This process is facilitated by a decrease in the electron-withdrawing properties of the dichlorophosphoryl moiety compared with the trichlorophosphonic group.…”