AIR-STABLE IMIDO ALKYLIDENE COMPLEXES AND USE THEREOF IN OLEFIN METATHESIS REACTIONS
The invention relates to Schrock-alkylidene complexes comprising a phenanthroline ligand. The complexes may dissociate when subjected to a solvent and release the complex being catalytically active in an olefinic metathesis reaction without needing a Lewis acid such as zinc chloride for removing the ligand. Thus, the phenanthroline complexes are autoactivating.
1 . Complex of formula I
wherein
M=Mo or W;
A is selected from N—R 1 or O, wherein R 1 is C 1-10 alkyl or aryl, optionally respectively substituted;
B is selected from pyrrole and pyrazole, optionally respectively substituted; or
B is C;
C is selected from O—R 2 , wherein R 2 is C 1-10 alkyl or aryl, optionally respectively substituted;
D is a neutral bidentate ligand, wherein said ligand is 1,10-phenanthroline or substituted 1,10-phenanthroline;
R 3 and R 4 are independently H, C 1-10 alkyl or aryl, C 1-10 alkyl and aryl being optionally substituted; and wherein only one of R 3 and R 4 is hydrogen.
2 . The complex of claim 1 , wherein the complex of formula I is characterized by a stability constant K with respect to the neutral ligand in a solvent, and wherein the substitution pattern of the complex of formula I in terms of at least one of D or C or D and C is selected such to adjust the stability constant K to a range of from 5 L*mol −1 to 250,000 L*mol −1 when measured at 298 K when the complex of formula I is dissolved in the solvent; preferably wherein the substation pattern of at least one of D or D and C is selected such to adjust the stability constant K to a range of from 5 L*mol −1 to 250,000 L*mol −1 when measured at 298 K when the complex of formula I is dissolved in the solvent.
3 . Complex of claim 1 or 2 , wherein
R 1 is C 1-10 alkyl or phenyl, respectively independently substituted with one or more of C 1-10 alkyl, C 1-10 alkoxy, phenyl, halogen, CN, and CF 3 .
4 . Complex of any one of the preceding claims, wherein B is pyrrole and pyrazole, respectively independently substituted with one or more of C 1-10 alkyl, C 1-10 alkoxy or phenyl.
5 . Complex of any one of claims 1 to 4 , wherein R 2 is selected from C 1-10 alkyl, independently substituted with one or more of halogen or phenyl; or is phenyl, independently substituted with one or more of C 1-10 alkyl, C 1-10 alkyl substituted with one or more of halogen, C 1-10 alkoxy, phenyl, halogen, —(CH 2 ) 4 — to form an annulated ring with said phenyl, or —(CH═CH—CH═CH)— to form an annulated ring with said phenyl, or with —O-silyl.
6 . Complex of any one of claims 1 to 5 , wherein phenanthroline is independently substituted with one or more electron-donating substituents, preferably selected from C 1-10 alkyl, C 1-10 alkoxy, phenyl, or is substituted with one or more electron-withdrawing substituents, preferably selected from halogen, CN, CF 3 and CCl 3 .
7 . Complex of any one of claims 1 to 6 , wherein R 3 and R 4 are independently H, C 1-10 alkyl or aryl, wherein C 1-10 alkyl or aryl are independently substituted with one or more of C 1-5 alkyl, C 1-5 alkyl substituted with one or more of halogen, C 1-5 alkoxy, phenyl, halogen.
8 . Complex of any one of claims 2 to 7 , wherein K is in the range of from 10 L*mol −1 to 150,000 L*mol −1 or 10 L*mol −1 to 100,000 L*mol −1 or 10 L*mol −1 to 50,000 L*mol −1 or 10 L*mol −1 to 10,000 L*mol −1 or 10 L*mol −1 to 5,000 L*mol −1 or 10 L*mol −1 to 500 L*mol −1 .
9 . Complex of any one of claims 2 to 8 , wherein the concentration of the complex in the solvent is in the range of from 0.0001 to 0.5 M.
10 . Complex of any one of claims 2 to 9 , wherein 1,10-phenanthroline and substituted 1,10 phenanthroline are selected in order to adjust K.
11 . Complex of any one of claims 2 to 10 , wherein 1,10-phenanthroline is substituted with one or more electron-donating groups in order to increase K compared to a complex of formula I having the same substitution pattern in terms of A, B and C but in which the bidentate ligand D is unsubstituted 1,10-phenanthroline.
12 . Complex of any one of claims 2 to 10 , wherein 1,10-phenanthroline is substituted with one or more electron-withdrawing groups in order to decrease K compared to a complex of formula I having the same substitution pattern in terms of A, B and C but in which the bidentate ligand D is unsubstituted 1,10-phenanthroline.
13 . Complex of any one of claims 2 to 12 , wherein C is selected in order to adjust K, wherein C is characterized in terms of its alkoxide cone angle, provided C is an alkoxide, the alkoxide cone angle and the determination thereof being defined in the description.
14 . Complex of claim 13 , wherein the alkoxide cone angle is increased in order to decrease K compared to a complex having the same substitution pattern in terms of A, B and D; or wherein the alkoxide cone angle is decreased in order to increase K compared to a complex having the same substitution pattern in terms of A, B and D.
15 . Complex of any one of claims 2 to 12 , wherein C is selected in order to adjust K, wherein C is characterized in terms of its steric bulk, provided C is an aryloxide.
16 . Complex of claim 15 , wherein the steric bulk is increased in order to decrease K compared to a complex having the same substitution pattern in terms of A, B and D; or wherein the steric bulk is decreased in order to increase K compared to a complex having the same substitution pattern in terms of A, B and D.
17 . Complex of any one of the preceding claims wherein the complex is of formula
wherein R is C(CH 3 ) 3 , C(CH 3 ) 2 C 6 H 5, C 6 H 5 , or o-(C 1-4 )-alkoxy C 6 H 4 ;
preferably wherein R is o-(C 1-4 )-alkoxy C 6 H 4 ;
more preferably wherein the complex is
[O-TBS=O-Si(t-butyl)(Me) 2 ].
18 . Method of making a complex as defined in any one of claims 1 to 17 , comprising:
subjecting a complex of formula II
wherein A, B, C, R 3 and R 4 have the meaning as defined with respect to the complex of formula I, to
1,10-phenanthroline or substituted 1,10-phenanthroline,
in the solvent.
19 . Method of claim 18 , further comprising isolating the complex of formula I in solid form.
20 . Method of claim 18 or 19 , wherein the complex of formula I is isolated by filtration.
21 . Method of claim 18 or 19 , wherein the complex of formula I is isolated by evaporating the solvent.
22 . System comprising
a complex of formula I as defined in any one of claims 1 to 17 and
a complex of formula II as defined in claim 18 ;
wherein the complex of formula I and the complex of formula II are dissolved in the solvent.
23 . System of claim 22 , wherein the system does not comprise a Lewis acid.
24 . System of claim 23 , wherein the Lewis acid is MgCl 2 , MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znl 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 .
25 . Method of making a complex of formula II as defined in claim 18 comprising:
dissolving the complex of formula I as defined in any one of claims 1 to 17 in the solvent.
26 . Method of claim 25 , wherein the method is performed in the absence of a Lewis acid.
27 . Method of claim 26 , wherein the Lewis acid is MgCl 2 , MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znl 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 .
28 . Method of performing a metathesis reaction of a compound comprising an olefinic double bond, comprising:
adding a complex as defined in any one of claims 1 to 17 to the olefinic compound in presence of the solvent.
29 . Method of claim 28 wherein the compound comprising an olefinic double bond is the solvent.
30 . Method of claim 28 or 29 , wherein the metathesis reaction is performed in absence of a Lewis acid.
31 . Method of claim 30 , wherein the Lewis acid is MgCl 2 , MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znl 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 .