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

Abstract

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 CMe2 -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 (ϕPL ) of 2.6 % (λem =600 nm), and an average lifetime (τ) of 4.8 μs. Reaction of 3 a with CuCl and AgOTf afforded (aryl)-(cyclic alkyl(imino)) phosphide-stabilized tetra-nuclear CuI (6), and octa-nuclear AgI (7) clusters, respectively. Moreover, complexes 3 a-3 c provided a direct route for the stabilization of cyclic alkyl(aminoboryl) phosphaalkenes 8 a-8 c when treated with 1-bromo-N,N,N',N'-tetraisopropylboranediamine.