The invention provides a process for the in-situ generation of a metathesis active catalyst of the formula:
1
comprising contacting an NHC carbene with a dimer of the formula [(arene)MX
1
X]
2
and an alkyne of the formula RC≡CR
1
or RC≡EC—CR
1
wherein
M is ruthenium or osmium;
X and X
1
are the same or different and are each independently an anionic ligand;
NHC is any N-heterocyclic carbene ligand; and,
R and R
1
are each independently hydrogen or a substituted or unsubstituted 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
alkylthio, C
1
-C
20
alkylsulfonyl and C
1
-C
20
alkylsulfinyl.
Preferably, the NHC is an s-IMES or IMES carbene ligand; the arene is preferably p-cymene and the alkyne is preferably acetylene. The invention further provides a process for ROMP and RCM reactions using the metathesis active catalysts.
该发明提供了一种原位生成配合物的方法,其配合物的
化学式为1,包括将NHC卡宾与
化学式为[(芳基)MX1X]2的二聚体和
化学式为RC≡CR1或RC≡
EC—CR1的
炔烃接触,其中M为
钌或
锇;X和X1相同或不同,均为独立的阴离子
配体;NHC为任何N-杂环卡宾
配体;R和R1各自独立地为氢或从C1-C20烷基,C2-C20烯基,C2-C20炔基,芳基,C1-C20
羧酸盐,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
硫基,C1-C20烷基磺酰基和C1-C20烷基亚磺酰基所选的取代或未取代基团。优选地,NHC为s-I
MES或I
MES卡宾
配体;芳基优选为p-环二
甲苯,
炔烃优选为
乙炔。该发明还提供了使用该交换活性催化剂进行ROMP和RCM反应的方法。