Diphosphametacyclophanes: Structural and Electronic Influences of Substituent Variation within a Family of Bis(diketophosphanyl) Macrocycles

Abstract

Article (Accepted Version) http://sro.sussex.ac.uk Pearce, Kyle G and Crossley, Ian R (2020) Diphosphametacyclophanes: structural and electronic influences of substituent variation within a family of bis(diketophosphanyl) macrocycles. Journal of Organic Chemistry.

The story of acyl phosphines: Synthesis, reactivity, and catalytic applications

“…[ 46 ] Recently, same group synthesized several macrocyclic bis (diketophosphanyl) compounds 39 (Chart 3) by the above methodology. [ 47,48 ] All compounds showed a single resonance in 31 P{ 1 H} NMR spectra in the region of δ 30–36 ppm, confirming the identical chemical environment around both phosphorus atoms. The spectra lie downfield in comparison with that of mono‐acyl phosphines due to the presence of two strong electron‐withdrawing carbonyl groups.…”

“…[46] Recently, same group synthesized several macrocyclic bis (diketophosphanyl) compounds 39 (Chart 3) by the above methodology. [47,48] All compounds showed a single resonance in 31 [49] The single crystal X-ray diffraction studies of compounds 30b, [50] 34(anti), 35d, 35e, 37a, 37b, 38b, 39, 40, and 41 were reported (representative examples are shown in Figure 2). The P-C(O) bond distance in 30b was found to be approximately 1.85 Å, and acyl C-O distances were found to be 1.20 Å.…”

Recent advances in organophosphorus–chalcogen and organophosphorus–pincer based macrocyclic compounds and their metal complexes

“…Phosphine-based pincer com-plexes are an important class of organometallic compounds with numerous catalytic applications [134][135][136] such as the formation of rare σ-methane complexes, 137 alkane dehydrogenation, 138 activation of C(sp 3 )-F bonds 139 R′ = I, Me, t Bu, Ph, and p-NCC 6 H 4 ), as described in Scheme 25. 141 The solid state structures of these cyclophanes (62a-e, 63 and 64) showed butterfly-like conformations with P-organyl substituents adopting mutually exo arrangements.…”

The unusual (syn-/anti-)2 conformation of a dimethoxypyrimidyl-based tennimide

“…Structural examples of the P-based crystal structures as VAWVIB and VAWVOH are available on the CSD (Groom et al, 2016). In addition, the highly constrained butterfly structures as 'dimers' have been reported as RAYFII and ZAFJAV (Saunders et al, 2012;Pearce & Crossley, 2020). He and co-workers in their structures NUKZIF, NULHOU, NULHUA (Wang et al, 2020) noted that such diimides and polyimides are still relatively rare (Wang et al, 2020).…”