[EN] FAR SUPERIOR OXIDATION CATALYSTS BASED ON MACROCYCLIC COMPOUNDS<br/>[FR] CATALYSEURS D'OXYDATION NETTEMENT SUPÉRIEURS À BASE DE COMPOSÉS MACROCYCLIQUES
申请人:UNIV CARNEGIE MELLON
公开号:WO2017053564A1
公开(公告)日:2017-03-30
An especially robust compound and its derivative metal complexes that are approximately one hundred-fold superior in catalytic performance to the previously invented TAML analogs is provided having the formula (I) wherein Y1, Y2, Y3 and Y4 are oxidation resistant groups which are the same or different and which form 5- or 6-membered rings with a metal, M, when bound to D; at least one Y incorporates a group that is significantly more stable towards nucleophilic attack than the organic amides of TAML activators; D is a metal complexing donor atom, preferably N; each X is a position for addition of a labile Lewis acidic substituent such as (i) H, deuterium, (ii) Li, Na, K, alkali metals, (iii) alkaline earth metals, transition metals, rare earth metals, which may be bound to one or more than one D, (iv) or is unoccupied with the resulting negative charge being balanced by a nonbonded counteraction; at least one Y may contain a site that is labile to acid dissociation, providing a mechanism for shortening complex lifetime. The new complexes deliver catalytic performances that promise to revolutionize multiple oxidation technology spaces including water purification.
提供了一种特别强大的化合物及其衍生金属配合物,其催化性能大约比先前发明的TAML类似物优越一百倍,其化学式为(I),其中Y1、Y2、Y3和Y4是抗氧化的基团,可以相同也可以不同,并且与金属M结合时形成5-或6-成员环;至少一个Y包含一个对亲核攻击更稳定的基团,比TAML活化剂的有机酰胺更稳定;D是金属络合给体原子,优选为N;每个X是用于添加易失去的Lewis酸性取代基的位置,例如(i)H、氘,(ii)Li、Na、K、碱金属,(iii)碱土金属、过渡金属、稀土金属,可以与一个或多个D结合,(iv)或者未被占据,由非键合的对应作用平衡产生的负电荷;至少一个Y可能包含一个易于酸解离的位点,提供缩短配合物寿命的机制。这些新配合物提供了催化性能,有望彻底改变多种氧化技术领域,包括水净化。