Tetracarbonyltungsten (0) and –molybdenum (0) complexes of P,N-containing cyclophanes

First Example of Cage P4N4-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu2I Fragments

“…Various 28-, 36-, 38- and 46-membered P,N-containing cyclophanes with 1,5-diaza-3,7-diphosphacyclooctane fragments incorporated into the macrocyclic backbone have been obtained by stereoselective covalent self-assembly between primary phosphines, formaldehyde, and diamines with spatially divided amino groups [ 19 , 20 , 21 , 22 , 23 , 24 , 25 ]. Later, their coordination properties towards metals of groups VI, VIII, and X have been studied [ 26 , 27 , 28 , 29 ]. In the uncoordinated cyclophanes, the eight-membered 1,5-diaza-3,7-diphosphacyclooctane fragments adopt a “crown” conformation in which the phosphorus electron lone pairs are directed inside the macrocycle cavity [ 20 , 22 , 23 , 24 , 25 ].…”

“…In the uncoordinated cyclophanes, the eight-membered 1,5-diaza-3,7-diphosphacyclooctane fragments adopt a “crown” conformation in which the phosphorus electron lone pairs are directed inside the macrocycle cavity [ 20 , 22 , 23 , 24 , 25 ]. It has been shown that complex formation with groups VI and VIII metals of these macrocycles led to dramatic changes in the initial conformations of the ligands; thus, the metal-containing moieties of the forming binuclear bis-P,P-chelate complexes were located outside the macrocyclic cavities [ 26 , 27 , 28 , 29 ]. Recently, it has been demonstrated that P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into the macrocyclic core form tetranuclear gold(I) complexes with gold(I) chloride with two of the four gold(I) ions located above and below the partially collapsed macrocyclic cavity [ 30 ].…”