Coordination chemistry of [2 + 2] Schiff-base macrocycles derived from the dianilines [(2-NH 2 C 6 H 4 ) 2 X] (X = CH 2 CH 2 , O): structural studies and ROP capability towards cyclic esters.

Reaction of the [2 + 2] Schiff-base macrocycles {[2-(OH)-5-(R)-C6H2-1,3-(CH)2][CH2CH2(2-C6H4N)2]}2 (R = Me, L1H2; tBu, L2H2) with FeBr2 afforded the complexes [FeBr(L1H2)]2[(FeBr3)2O]·2MeCN (1·2MeCN), [FeBr(L2H2)][X] (X = 0.5(FeBr3)2O, 2·0.5MeCN, X = Br, 3·5.5MeCN), respectively. Reaction of L2H2 with [KFe(OtBu)3(THF)] (formed in situ from FeBr2 and KOtBu), following work-up, led to the isolation of the complex [Fe(L2)(L2H)]·3MeCN (4·3MeCN), whilst with [CuBr2] afforded [CuBr(L2H2)][CuBr2]·2MeCN (5·2MeCN). Attempts to form mixed Co/Ti species by reaction of [CoBrL2][CoBr3(NCMe)] with TiCl4 resulted in [L2H4][CoBr4]·2MeCN (6·2MeCN). Use of the related oxy-bridged Schiff-base macrocycles {[2-(OH)-5-(R)-C6H2-1,3-(CH)2][O(2-C6H4N)2]}2 (R = Me, L3H2; tBu, L4H2) with CoBr2 led to the isolation of the complexes [(CoBr)2(L3)]·2C3H6O (7·2C3H6O), [Co(NCMe)2(L4H2)][CoBr4]·5MeCN (8·5MeCN), [Co(NCMe)6][CoBr3(MeCN)]2·2MeCN (9·2MeCN). For comparative structural/polymerisation studies, the complexes {CoBr(NCMe)L5}2·2MeCN (10·2MeCN) and [Co(NCMe)2L5]2[CoBr3(NCMe)]2 (11), [FeBr(NCMe)L5]2·2MeCN (12·2MeCN) where L5H = 2,6-(CHO)2-4-tBu-C6H2OH, as well as the chelate-free salt [Fe(NCMe)6][FeBr3OFeBr3] (13) have been isolated and structurally characterized. The ability of these complexes to act as catalysts for the ring opening polymerisation (ROP) of ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) was investigated, as well as co-polymerisation of ε-CL with rac-lactide (r-LA) and vice versa.