申请人:CALIFORNIA INSTITUTE OF TECHNOLOGY
公开号:US20160237101A9
公开(公告)日:2016-08-18
The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of the formula
wherein:
M is ruthenium or osmium;
X and X
1
are each independently an anionic ligand;
L is a neutral electron donor ligand; and,
R, R
1
, R
6
, R
7
, R
8
, and R
9
are each independently hydrogen or a substituent selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthiol, aryl thiol, C
1
-C
20
alkylsulfonyl and C
2
-C
20
alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C
1
-C
10
alkyl, C
1
-C
10
alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.
本发明涉及一种新型的以咪唑啉为基础的配体的交换催化剂以及其制备和使用方法。该创新催化剂的化学式为:其中,M为钌或锇;X和X1分别为独立的阴离子配体;L为中性电子供体配体;R、R1、R6、R7、R8和R9分别为氢或选自以下基团的取代基:C1-C20烷基、C2-C20烯基、C2-C20炔基、芳基、C1-C20羧酸酯、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、芳氧基、C2-C20烷氧羰基、C1-C20烷基硫醇、芳基硫醇、C1-C20烷基磺酰基和C2-C20烷基亚磺酰基,所述取代基可选地被一个或多个选自以下基团的取代基所取代:C1-C10烷基、C1-C10烷氧基、芳基和羟基、硫醇、硫醚、酮、醛、酯、醚、胺、亚胺、酰胺、硝基、羧酸、二硫化物、碳酸酯、异氰酸酯、碳酸酰基、卡波酯、卡巴酰胺和卤素的官能团。在以前所述的钌或锇催化剂中加入咪唑啉配体被发现可以显著改善这些配合物的性质。这种创新催化剂保持了以前所描述的钌配合物的官能团耐受性,同时具有增强的交换活性,与先前的钨和钼系统相比具有更好的性能。