Method for producing 3,7-diaza-bicyclo[3.3.1]nonane metal complexes
The invention relates to a method for producing metal complexes of formula (2) [M a L x X n ]Y m (2), where M is a metal from the group consisting of Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III) or Fe(IV), X is a coordinating compound selected from mono-, bi- or tri-charged anions or neutral molecules which can coordinate to a metal in mono-, bi- or tri-dentate form, Y represents a non-coordinating counter-ion which ensures charge equalization of the complex, L represents a ligand of formula (1) or the protonized or de-protonized form thereof, and a, x, n, m, R, R 1 , R 2 , R 3 and z have the meanings described in claim 1 . Said method is characterized in that the reaction of one or more ligands of formula (1) with an iron salt or manganese salt is carried out in an acetone/water mixture in a temperature range from 0 to 50° C. and for this purpose a solution or a suspension of the one or more ligands of formula (1) in acetone is brought in contact with an aqueous metal salt solution of the iron salt or manganese salt in the temperature range in which the reaction takes place.
1. A process for preparing at least one metal complex of the formula (2)
[M a L x X n ]Y m (2)
where
M is a metal selected from the group consisting of Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III) and Fe(IV),
X is a coordinating compound selected from the group consisting of singly, doubly and triply charged anions and uncharged molecules capable of mono-, bi- or tridentate coordination to a metal,
Y is a noncoordinating counterion which ensures the charge balance of the complex,
a is 1 or 2,
x is 1 or 2,
n is a number from 0 to 4,
m is a number from 0 to 8, and
L is a ligand of the formula (1) or the protonated or deprotonated form thereof
where
R is hydrogen, hydroxyl or C 1 -C 4 alkyl;
R 1 is C 1 -C 4 alkyl, C 6 -C 10 aryl, pyridinyl-C 1 -C 4 -alkyl or (CH 2 ) k N(C 1 -C 4 -alkyl) 2 ;
R 2 is C 1 -C 20 alkyl, C 6 -C 10 aryl or pyridinyl-C 1 -C 4 -alkyl;
R 3 is C 1 -C 4 alkyl;
z is C═O or C(OH) 2 and
k is a number from 1 to 6,
comprising the steps of
(i) preparing a solution or suspension of at least one ligand of formula (1) in acetone;
(ii) preparing an aqueous metal salt solution of an iron or manganese salt;
(iii) contacting the solution or suspension of at least one ligand of formula (1) in acetone with the aqueous metal salt solution of the iron or manganese salt; and
(iv) reacting the at least one ligand of the formula (1) with the iron or manganese salt in an acetone/water mixture wherein the temperature range is from 0 to 50° C.
2. The process as claimed in claim 1 , wherein X is selected from the group consisting of OH − , NO 3 − , NO, S 2− , R a S − , PO 4 3− , H 2 O, CO 3 2− , R b OH, Cl − , Br − , CN − , ClO 4 − , R a COO − and SO 4 2− , where R a is H or C 1 -C 4 alkyl and R b is C 1 -C 4 alkyl.
3. The process as claimed in claim 1 , wherein Y is selected from the group consisting of R c SO 4 − , SO 4 2− , NO 3 − , Cl − , Br − , I − , ClO 4 − , BF 4 − , PF 6 − and R c SO 3 − , where R c is H or C 1 -C 4 alkyl.
4. The process as claimed in claim 1 , wherein the temperature range is from 5 to 35° C.
5. The process as claimed in claim 1 , wherein at least one complex of the formula [FeLCl]Cl, [FeL(SO 4 )], [MnLCl]Cl, [MnL(SO 4 )], [FeLCl]PF 6 , [FeL(H 2 O)][PF 6 ] 2 or [FeL(H 2 O)][BF 4 ] 2 is prepared, where L is selected from the group consisting of
dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o),
dimethyl 2,4-di(2-pyridyl)3-(pyridin-2-ylmethyl)-7-methyl-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3u),
diethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate,
dimethyl 2,4-di(2-pyridyl)-3,7-bis(pyridin-2-ylmethyl)-3,7-diazabicyclo-[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py4),
dimethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py2),
diethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate,
dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(N,N′-dimethylethylamine)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate
and the corresponding dihydroxy ketals.
6. The process as claimed in claim 1 , wherein the at least one ligand of the general formula (1) is selected from the group consisting of dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o), dimethyl 2,4-di(2-pyridyl)-3,7-dimethyl-3,7-diazabicyclo-[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py2) and the corresponding dihydroxy ketals.
7. The process as claimed in claim 2 , wherein X is selected from the group consisting of Cl − and SO 4 2− .
8. The process as claimed in claim 3 , wherein Y is selected from the group consisting of Cl − and SO 4 2− .
9. The process as claimed in claim 1 , wherein the iron or manganese salt used is a metal(II) salt.
10. The process as claimed in claim 9 , wherein the metal(II) salt is selected from the group consisting of iron(II) chloride, iron(II) sulfate, manganese(II) chloride and manganese(II) sulfate.
11. The process as claimed in claim 10 , wherein the metal(II) salt is iron(II) chloride.
12. The process as claimed in claim 1 , wherein at least one complex of the formula [FeLC]Cl is prepared, wherein L is dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2Py3o) or the corresponding dihydroxy ketal, and dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]-nonan-9-one-1,5-dicarboxylate or the corresponding dihydroxy ketal, or mixtures thereof, by the step of reacting L with iron(II) chloride.
13. The process as claimed in claim 1 , wherein the weight ratio of acetone:ligand of the formula (1) is from 15.0:1.0 to 0.5:1.0.
14. The process as claimed in claim 1 , wherein the molar ratio of ligand of the formula (1):metal salt is from 0.9:1.0 to 1.2:1.0.
15. The process as claimed in claim 1 , wherein the metal salt in aqueous solution is used in a concentration of 10 to 50% by weight.
16. The process as claimed in claim 2 , wherein Y is Cl − .
17. The process as claimed in claim 3 , wherein Y is Cl − .