Method for producing aqueous preparations of complexes of platinum group metals
The invention relates to a method for producing aqueous preparations of complexes of platinum group metals (PGM) Pt, Pd, Rh and Ir having the general formula [M A /M B /M C (L) a (H 2 O) b (O 2 —) c (OH − ) d ](OH—) e (H + ) f , wherein M A =Pt II or Pd II , M B =Pt IV , M C =Rh or Ir, L is a neutral monodentate or bidentate donor ligand, and a is an integer between 1 and 4 (or 2) and/or between 1 and 6 (or 3), b is an integer between 0 and 3 (or 5), c is an integer between 0 and 3 (or 4), d is an integer between 0 and 3 (or 5), e is an integer between 0 and 2 (or 3 or 4) and f is an integer between 0 and 4 (or 5). In the method according to the invention, the hydroxo complexes H 2 P d (OH) 4 (in the case of M A =Pd II ), H 2 Pt(OH) 6 (in the case of M A =Pt II and M B =Pt IV ) or H 3 M C (OH) 6 (for M C =Rh III Ir III ) are converted in the presence of the donor ligands, wherein at least one hydroxo group of the hydro complex is exchanged. Preferably, the reaction occurs at temperatures in the range of 40 to 110° C. with a reaction time of between 2 and 24 hours, wherein, where MA=PtII, the conversion additionally occurs in the presence of a reduction agent. The method optionally further comprises an exchange of OH anions bound outside of the complex sphere with other anions (e.g. hydrogen carbonate or carbonate anions). The aqueous preparations contain PGM complexes such as [Pt(en) 2 ](OH) 2 , [Pt(EA) 4 ](OH) 2 or [Rh(NH 3 ) 6 ](OH) 3 and are used to produce electroplating baths, heterogeneous catalysts or metal powders, for example.
1. A process for producing water-containing preparations of complexes of the platinum group metals (PGM) having the general formula (1), (2) or (3)
[M A (L) a (H 2 O) b (O 2− ) c (OH − ) d ](OH − ) e (H + ) f (1)
where
M A =platinum (Pt) or palladium (Pd) in the oxidation state +2 and
L=an uncharged monodentate or bidentate donor ligand and
a=an integer from 1 to 4 (for monodentate donor ligands) or an integer from 1 to 2 (for bidentate donor ligands),
b=an integer from 0 to 3,
c=an integer from 0 to 3,
d=an integer from 0 to 3,
e=an integer from 0 to 2 and
f=an integer from 0 to 4
and the platinum group metal M A has the coordination number 4,
wherein the hydroxo complexes H 2 Pd(OH) 4 (in the case of M A =Pd) or H 2 Pt(OH) 6 (in the case of M A =Pt) are in each case reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex concerned is replaced and in the case of M A =Pt the reaction is carried out in the presence of a reducing agent
or
[M B (L) a2 (H 2 O) b2 (O 2− ) c2 (OH − ) d2 ](OH − ) e2 (H + ) f2 (2)
where
M B =platinum (Pt) in the oxidation state +4 and
L=an uncharged monodentate or bidentate donor ligand and
a2=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b2=an integer from 0 to 5,
c2=an integer from 0 to 4,
d2=an integer from 0 to 5,
e2=an integer from 0 to 4 and
f2=an integer from 0 to 4
and the platinum group metal M B has the coordination number 6,
wherein the hydroxo complex H 2 Pt(OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced
or
[M C (L) a3 (H 2 O) b3 (O 2− ) c3 (OH − ) d3 ](OH − ) e3 (H + ) f3 (3)
where
M C =rhodium (Rh) or iridium (Ir) in the oxidation state +3 and
L=an uncharged monodentate or bidentate donor ligand and
a3=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b3=an integer from 0 to 5,
c3=an integer from 0 to 4,
d3=an integer from 0 to 5,
e3=an integer from 0 to 3 and
f3=an integer from 0 to 5
and the platinum group metal M C has the coordination number 6,
wherein a hydroxo complex of the type H 3 M C (OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced and
wherein the water-containing preparations have a pH in the range of 5 to 14.
2. The process as claimed in claim 1 , wherein the PGM has the general formula (1).
3. The process as claimed in claim 1 , wherein the PGM has the general formula (2).
4. The process as claimed in claim 1 , wherein the PGM has the general formula (3).
5. The process as claimed in claim 1 , wherein the indices a-f in the general formulae (1), a2-af2 in formula (2) or a3-f3 in formula (3) are selected so that the resulting PGM complexes are electrically neutral.
6. The process as claimed in claim 1 , wherein the reaction temperature is in the range from 40 to 110° C.
7. The process as claimed in claim 1 , wherein the reaction time is in the range from 2 to 24 hours.
8. The process as claimed in claim 1 , wherein said monodentate donor ligands are ammonia or ligands selected from the group consisting of monoalkylamines, dialkylamines, trialkylamines, monoalkanolamines, dialkanolamines, trialkanolamines, monoarylamines, diarylamines, triarylamines, trialkylphosphines, triarylphosphines, trialkoxyphosphines, triaryloxyphosphines and mixtures thereof.
9. The process as claimed in claim 7 , wherein said monodentate donor ligands are ammonia, ethanolamine, ethylamine, diethylamine, isopropanolamine or mixtures thereof.
10. The process as claimed in claim 1 , wherein said bidentate donor ligands are alkylenediamines, arylenediamines, alkylenediphosphines, arylenediphosphines or mixtures thereof.
11. The process as claimed in claim 10 , wherein said bidentate donor ligands are ethylenediamine, o-phenylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine or mixtures thereof.
12. The process as claimed in claim 1 , wherein the replacement of the OH groups in the hydroxo complexes H 2 Pd(OH) 4 , H 2 Pt(OH) 6 or H 3 M C (OH) 6 (in the case of M C =Rh III or Ir III ) by the uncharged donor ligands L is incomplete and the resulting compounds of the general formulae (1), (2) or (3) continue to contain aquo (H 2 O), oxo (O 2− ) or hydroxo (OH − ) ligands.
13. The process as claimed in claim 1 , wherein hydrogen, an H 2 /N 2 mixture, hydrazine (N 2 H 4 ), oxalic acid (H 2 C 2 O 4 ), formaldehyde (HCHO) or formic acid (HCOOH) or mixtures thereof are used as reducing agent in the case of M A =platinum(II).
14. The process as claimed in claim 1 , wherein the water-containing preparations are aqueous solutions and the reaction is carried out in aqueous solution.
15. The process as claimed in claim 1 , wherein the water-containing preparations contain organic solvents and the reaction is carried out in water-containing solvent mixtures.
16. The process as claimed in claim 1 , wherein the concentration of the platinum group metals M A , M B or M C in the water-containing preparation is in the range from 0.5 to 15% by weight.
17. The process as claimed in claim 1 , wherein the total halogen content, in particular the total chlorine content, of the preparations is <5000 ppm (in each case based on the PGM content).
18. The process as claimed in claim 1 which further comprises replacement of the OH anions (OH − ) e in the PGM complexes of the general formulae
[M A (L) a (H 2 O) b (O 2− ) c (OH − ) d ](OH − ) e (H + ) f (1),
[M B (L) a2 (H 2 O) b2 (O 2− ) c2 (OH − ) d2 ](OH − ) e2 (H + ) f2 (2)
[M C (L) a3 (H 2 O) b3 (O 2− ) c3 (OH − ) d3 ](OH − ) e3 (H + ) f3 (3)
by one or more anions of inorganic or organic acids (where the meanings of M A , M B , M C , L, a, b, c, d, e, f, a2, b2, c2, d2, e2, f2, a3, b3, c3, d3, e3, and f3 are as defined in claim 1 and e, e2 and e3≠0).
19. The process as claimed in claim 18 , wherein the anions of inorganic or organic acids are acetates, formates, oxalates, carbonates, hydrogencarbonates, sulfates, nitrates, phosphates, tetrafluoroborates or mixtures thereof.
20. A process for producing water-containing preparations of complexes of the platinum group metals (PGM) having the general formula (1), (2) or (3)
[M A (L) a (H 2 O) b (O 2− ) c (OH − ) d ](OH − ) e (H + ) f (1)
where
M A =platinum (Pt) or palladium (Pd) in the oxidation state +2 and
L=an uncharged monodentate ligand or a bidentate donor ligand wherein the monodenate ligand is ammonia or ligands selected from the group consisting of monoalkylamines, dialkylamines, trialkylamines, monoalkanolamines, dialkanolamines, trialkanolamines, monoarylamines, diarylamines, triarylamines, trialkylphosphines, triarylphosphines, trialkoxyphosphines, triaryloxyphosphines and mixtures thereof or bidentate donor ligand and
a=an integer from 1 to 4 (for monodentate donor ligands) or an integer from 1 to 2 (for bidentate donor ligands),
b=an integer from 0 to 3,
c=an integer from 0 to 3,
d=an integer from 0 to 3,
e=an integer from 0 to 2 and
f=an integer from 0 to 4
and the platinum group metal M A has the coordination number 4,
wherein the hydroxo complexes H 2 Pd(OH) 4 (in the case of M A =Pd) or H 2 Pt(OH) 6 (in the case of M A =Pt) are in each case reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex concerned is replaced and in the case of M A =Pt the reaction is carried out in the presence of a reducing agent
or
[M B (L) a2 (H 2 O) b2 (O 2− ) c2 (OH − ) d2 ](OH − ) e2 (H + ) f2 (2)
where
M B =platinum (Pt) in the oxidation state +4 and
L=is defined above and
a2=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b2=an integer from 0 to 5,
c2=an integer from 0 to 4,
d2=an integer from 0 to 5,
e2=an integer from 0 to 4 and
f2=an integer from 0 to 4
and the platinum group metal M B has the coordination number 6,
wherein the hydroxo complex H 2 Pt(OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced
or
[M C (L) a3 (H 2 O) b3 (O 2− ) c3 (OH − ) d3 ](OH − ) e3 (H + ) f3 (3)
where
M C =rhodium (Rh) or iridium (Ir) in the oxidation state +3 and
L=is defined above and
a3=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b3=an integer from 0 to 5,
c3=an integer from 0 to 4,
d3=an integer from 0 to 5,
e3=an integer from 0 to 3 and
f3=an integer from 0 to 5
and the platinum group metal M C has the coordination number 6,
wherein a hydroxo complex of the type H 3 M C (OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced.
21. A process for producing water-containing preparations of complexes of the platinum group metals (PGM) having the general formula (1), (2) or (3)
[M A (L) a (H 2 O) b (O 2− ) c (OH − ) d ](OH − ) e (H + ) f (1)
where
M A =platinum (Pt) or palladium (Pd) in the oxidation state +2 and
L=bidentate donor ligand, said bidentate donor ligand is alkylenediamine, arylenediamine, alkylenediphosphine, arylenediphosphine or mixtures thereof, and
a=an integer from 1 to 2 (for bidentate donor ligands),
b=an integer from 0 to 3,
c=an integer from 0 to 3,
d=an integer from 0 to 3,
e=an integer from 0 to 2 and
f=an integer from 0 to 4
and the platinum group metal M A has the coordination number 4,
wherein the hydroxo complexes H 2 Pd(OH) 4 (in the case of M A =Pd) or H 2 Pt(OH) 6 (in the case of M A =Pt) are in each case reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex concerned is replaced and in the case of M A =Pt the reaction is carried out in the presence of a reducing agent
or
[M B (L) a2 (H 2 O) b2 (O 2− ) c2 (OH − ) d2 ](OH − ) e2 (H + ) f2 (2)
where
M B =platinum (Pt) in the oxidation state +4 and
L=defined above and
a2=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b2=an integer from 0 to 5,
c2=an integer from 0 to 4,
d2=an integer from 0 to 5,
e2=an integer from 0 to 4 and
f2=an integer from 0 to 4
and the platinum group metal M B has the coordination number 6,
wherein the hydroxo complex H 2 Pt(OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced
or
[M C (L) a3 (H 2 O) b3 (O 2− ) c3 (OH − ) d3 ](OH − ) e3 (H + ) f3 (3)
where
M C =rhodium (Rh) or iridium (Ir) in the oxidation state +3 and
L=defined above and
a3=an integer from 1 to 6 (for monodentate donor ligands) or an integer from 1 to 3 (for bidentate donor ligands),
b3=an integer from 0 to 5,
c3=an integer from 0 to 4,
d3=an integer from 0 to 5,
e3=an integer from 0 to 3 and
f3=an integer from 0 to 5
and the platinum group metal M C has the coordination number 6,
wherein a hydroxo complex of the type H 3 M C (OH) 6 is reacted with an uncharged donor ligand L, where at least one hydroxo group of the hydroxo complex is replaced.
22. The process as claimed in claim 21 , wherein the water-containing preparations have a pH in the range of 7 to 14.
23. The process as claimed in claim 1 , wherein the water-containing preparations have a pH in the range of 7 to 12.
24. The process as claimed in claim 20 , wherein the water-containing preparations have a pH in the range of 5 to 14.