Phosphacyclanes in reactions of bis(ortho-formylphenyl)phenylthioxophosphonate with diamines

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

“…132 The reaction of 56 (56 was previously reported by Chivers and co-workers 133 ) with an excess of elemental Se in toluene under refluxing conditions produced an unexpected product P 4 (μ-N t Bu) 3 (μ-NH) 3 Se 4 (59) instead of [{P(Se) (μ-N t Bu)} 2 (μ-N t Bu)] 2 (58) (Scheme 23). The solid-state structure of P 4 (μ-N t Bu) 3 (μ-NH) 3 Se 4 (59) shows a tetraselenide macrocycle comprising three tert-butyl groups, two on the ring-bridging nitrogen atoms and one on the P 2 N 2 ring, which indicates unexpected C-N bond cleavage and N-H bond formation. In contrast, the oxidation of the less sterically hindered 57 yielded P 4 (μ-N i Pr) 5 (μ-NH)Se 4 (60) with the loss of only one sub-stituent.…”

“…58 These macrocycles are synthesized by reacting the hydrazides of thiophosphonic and phosphonic acids with dialdehydes. Burilov and co-workers prepared macrocycles 1-3 containing P-O 59 The synthesis of unsymmetrical phosphorus(III)-arene macrocycles (4 and 5) via the phosphorylation reaction was reported by Abramov and co-workers. 60 Under solvent-free conditions, bisphenols III and IV were reacted with two equivalents of phosphonous diamide to afford bisphosphonoamidites V and VI, which were again reacted with IV and III, respectively, to form unsymmetrical phosphorus(III)-arene macrocycle 4 as shown in Scheme 2.…”