Probing the Group Tolerance of a Li/Cl Phosphinidenoid Complex Using Alkenyl-Substituted Aldehydes

Abstract

Reaction of the Li/Cl phosphinidenoid pentacarbonyltungsten complex 2 (R = CH(SiMe 3 ) 2 ) with unsaturated aldehydes 3, 4, 9, 10, and 13 yielded the new oxaphosphirane complexes 5, 7, 11, 12, and 14 and thus revealed a clear preference for CO vs CC bond addition (i) and for 1,2-vs 1,4 addition (ii). Complexes were characterized by NMR, IR spectroscopy, and mass spectrometry and, in the case of 14a, by single-crystal X-ray analysis.

1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

“…So far, structural information is available exclusively for the P –F derivative [Li­(12-crown-4)­(Et 2 O)]­[(CO) 5 WP­{(CH­(SiMe 3 ) 2 F}], for which a single-crystal structure was obtained revealing the molecular structure of a salt with distinct ions. In the following years, the closed-shell reactivity of Li/Cl phosphinidenoid complexes toward organic halides, alkynes, aldehydes, , ketones, imines, and alcohols were studied yielding a broad spectrum of complexes with new and novel P-ligands.…”

Thiaphosphiranes and Their Complexes: Systematic Study on Ring Strain and Ring Cleavage Reactions

“…Whereas unligated oxaphosphiranes, having a CPO ring (standing for a three-membered ring constituted by a C, a P, and a O atom) and a P III center, are completely unknown, the chemistry of azaphosphiridines and thiaphosphiranes, having CPN and CPS rings, respectively, is still largely underdeveloped, and only diphosphiranes, having a CP 2 ring, have been investigated in greater detail. Recently, pentacarbonyl metal complexes of group 6 elements (Cr, Mo, W) of oxaphosphiranes , and azaphosphiridines became easily accessible using the versatile Li/Cl phosphinidenoid complex methodology, thus enabling intense studies on closed- and open-shell chemistry of the CPO and CPN rings . It is worth mentioning that studies related with the theoretical exploration of the potential energy surface (PES) of these ring systems have provided valuable information about relative stabilities of isomers, ring strain energies, and, very interestingly, to eventual bond weakening upon simple transformations such as protonation, complexation, one-electron oxidation, and/or reduction. , …”

Synthesis of Li/OR phosphinidenoid complexes: on the evidence for intramolecular O–Li donation and the effect of cation encapsulation

“…residual electron density = 0.604/ −0.781 e Å −3 .Crystal structure data of complex 13b (C 16 H 19 O 6 PW) Crystal size 0.30 × 0.16 × 0.1 mm, triclinic, P1 ˉ, a = 8.5181(5), b = 8.6529(5), c = 13.6246(8) Å, α = 93.925(5), β = 99.505(5), γ = 108.288(4)°, V = 932.62(9) Å 3 , Z = 2, ρ calc = 1.859 Mg m −3 , 2θ max = 56°, collected (independent) reflections = 9446 (4463), R int = 0.0348, μ = 6.305 mm −1 , 226 refined parameters, 3 restraints, R 1 (for I > 2σ(I)) = 0.0199, wR 2 (for all data) = 0.0515, max./min. residual electron density = 1.061/−1.433 e Å −3 .Crystal structure data of complex 14a (C 15 H 25 O 6 PSi 2 W) Crystal size 0.27 × 0.21 × 0.10 mm, monoclinic, P2 1 /a, a = 14.8631(7), b = 9.4639(3), c = 16.6281(9) Å, α = 90, β = 106.845(4), γ = 90°, V = 2238.60(18) Å 3 , Z = 4, ρ calc = 1.698 Mg m −3 2θ max = 56°, collected (independent) reflections = 11 102 (5275), R int = 0.0389, μ = 5.363 mm −1 , 235 refined parameters, 3 restraints, R 1 (for I > 2σ(I)) = 0.0222, wR 2 (for all data) = 0.0499, max./min. residual electron density = 0.789/ −1.282 e Å −3 .…”