Isolation of (Aryl)-(Imino) Phosphide and (Aryl)-(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene-Phosphinidenes under Reductive-Thermal Rearrangements.

Invited for the cover of this issue are Sudipta Roy and co-workers at the Indian Institute of Science Education and Research (IISER) Tirupati. The image depicts the rearrangement of cyclic alkyl(amino) carbene (cAAC)-supported chloro-phosphinidenes affording two ligands, of which one was used for the solid-state isolation of three cyclic alkyl(amino-boryl) phosphaalkenes and two coinage metal clusters. Read the full text of the article at 10.

Isolation of (Aryl)-(Imino) Phosphide and (Aryl)-(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene-Phosphinidenes under Reductive-Thermal Rearrangements.

Two-electron reduction of cyclic alkyl(amino) carbene (cAAC)-supported chloro-phosphinidene cAAC=P-Cl (1) followed by unprecedented thermal rearrangements afforded the alkali metal complexes of (aryl)-(cyclic alkyl(imino)) phosphides 3 a-3 c, 4 a-4 b through migration of the 2,6-diisopropylphenyl (dipp) group from N to the P centre, and the (aryl)-(cyclic alkyl(phosphaalkene)) amide 5 through cleavage of the CMe -N bond followed by energetically favoured 5-exo-tet ring-closure in the presence of the alkali metals Cs (3 a-3 c), K (4 a, 4 b), and Li (5). Compound 3 a was found to be photoluminescent (PL), emitting bright orange light under a laboratory UV lamp of wavelength 365 nm with PL quantum yield (ϕ ) of 2.6 % (λ =600 nm), and an average lifetime (τ) of 4.