Complexes useful as active components in supported epoxidation catalysts

摘要

Method of preparing epoxidation catalysts are disclosed, including methods comprising reacting an inorganic siliceous solid with a metal complex of the formulas:;
wherein the variables are defined herein.

主权项

1. A method of preparing a catalyst, comprising:
(a) contacting an inorganic siliceous solid with a metal complex of the formula: wherein:
L1 is alkoxy(C≦8), aryloxy(C≦16), aralkoxy(C≦16), or a substituted version of any of these groups, or L1 is taken together with L2 as defined below, or L1 is taken together with L2 and L3 as defined below;L2 is alkoxy(C≦8), aryloxy(C≦16), aralkoxy(C≦16), or a substituted version of any of these groups, or L2 is taken together with L1 as defined below, or L2 is taken together with L1 and L3 as defined below;L3, if present, is alkoxy(C≦8), aryloxy(C≦16), aralkoxy(C≦16), or a substituted version of any of these groups, or L3 is taken together with L1 and L2 as defined below:L1 and L2, when taken together, are a group of the formula: wherein: R″ and R″′ are each independently —H, alkyl(C≦8), alkenyl(C≦8), alkynyl(C≦8), aryl(C≦12), aralkyl(C≦12), heteroaryl(C≦8), heterocycloalkyl(C≦12), or a substituted versions of any of these groups other than —H; and Ar1 and Ar2 are each independently arenediyl(C≦16) or substituted arenediyl(C≦16);L1, L2 and L3, when taken together, are a group of the formula: wherein: R″ is —H, alkyl(C≦8), alkenyl(C≦8), alkynyl(C≦8), aryl(C≦12), aralkyl(C≦12), heteroaryl(C≦8), heterocycloalkyl(C≦12), or a substituted versions of any of these groups other than —H; and Ar1, Ar2, and Ar3 are each independently arenediyl(C≦16) or substituted arenediyl(C≦16);X1, X2, and X3 are each chloro;R′ is each independently:
—H, —OH, —SH, —CN, —F, —CF3, —NH2, —Si(CH3)2Cl, or —Si(CH3)2—Cp—Si(CH3)2Cl, oralkyl(C≦8), alkenyl(C≦8), alkynyl(C≦8), aryl(C≦12), aralkyl(C≦12), heteroaryl(C≦8), heterocycloalkyl(C≦12), or a substituted versions of any of these groups; ortwo or more pairs of R′ are taken together to form an alkenediyl(C≦8) or a substituted alkenediyl(C≦8); andn is 0 to 5;
to form a metal complex inorganic siliceous solid mixture; and (b) calcining the mixture from step (a) between 200 ° C. to 400 ° C. under conditions suitable to form a catalyst comprising the metal from the metal complex attached to the inorganic siliceous solid;
with the proviso that the method does not comprise a calcining step at a temperature greater than 400 ° C.