Selection of the cis and trans phosph(iii)azane macrocycles [{P(µ-NtBu)}2(1-Y-2-NH-C6H4)]2(Y = O, S)

Abstract

The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans). Model M.O. calculations suggest that the selection of the cis and trans isomers is not thermodynamically controlled. The alternative isomers 1.trans and 2.cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H4)P(mu-NtBu)]2[Y=O (3), S (4)] with nBuLi followed by cyclisation with [ClP(mu-NtBu)]2. The solid-state structures of 1.cis/trans(50 : 50), 2.cis, 3 and 4 are reported.

Mechanochemical Synthesis of Phosphazane‐Based Frameworks

“…This is in contrast to the previous observations by Wright et al. by using asymmetric linkers, where reactions of compound 1 with 2‐aminophenol or 2‐aminothiophenol produced a mixture of both cis and trans isomers . The exclusive formation of the trans products 5 and 6 suggest that the reaction most likely proceeds through the initial formation of a monosubstituted intermediate .…”

“…by using asymmetric linkers, where reactions of compound 1 with 2‐aminophenol or 2‐aminothiophenol produced a mixture of both cis and trans isomers . The exclusive formation of the trans products 5 and 6 suggest that the reaction most likely proceeds through the initial formation of a monosubstituted intermediate . In the case of the reactions of compound 1 with isophthalic and terephthalic acids, only one product was obtained as indicated by the presence of a singlet signal at δ =164.8 and 188.0 ppm for compounds 7 and 8 , respectively (compare δ =207.0 ppm for compound 1 ).…”

“…Interestingly, the in-situ 31 [62] The exclusive formation of the trans products 5 and 6 suggestt hat the reaction most likely proceeds through the initial formation of am onosubstituted intermediate. Interestingly, the in-situ 31 [62] The exclusive formation of the trans products 5 and 6 suggestt hat the reaction most likely proceeds through the initial formation of am onosubstituted intermediate.…”

Transition metal complexes of 13- and 14-membered N2O2 macrocycles: synthesis and characterization

“…Recent studies on macrocyclic complexes containing mixed nitrogen, sulfur, and/or oxygen donor atoms [3][4][5][6][7][8] show that it remains an active area of research. Elegant studies on ligand design and metal ion recognition of macrocyclic complexes have been reported by Lindoy [9][10][11] and co-workers.…”

N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks

“…The majority of the efforts made in cyclodiphosphazane chemistry have been focused on the synthesis of both hybrid and fully inorganic cyclic cyclodiphosphazane species due to their potential applications in host–guest chemistry [31f,g, 32–39] . In contrast, there have been limited attempts to synthesise complex acyclic, chain‐like, poly‐cyclodiphosphazane (poly‐P 2 N 2 ) oligomers (i.e., dimers, trimers, etc.…”