RU2329269C2 - Method of obtaining cation complexes of palladium - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining cation complexes of palladium, containing organic or element-organic acidoligands with general formula [LPdL'₂]A, where L is acetylacetonate (Acac), L' represents tertiary phosphines of the triphenylphosphine, triorthotolylphosphine, triparatolylphosphine, triorthoanisylphosphine type etc, A represents anions of the BF₄, F₃CSO₃ type, used as catalysts in a telomerisation reaction of isoprene and diutylamine, as welll as components of catalyst systems in the selective dimerisation of styrene. The method involves reaction of components: bis(acetylacetonate)palladium, Pd(Acac)₂; tertiary phosphine, PR₃; boron trifluoride etherate BF₃OEt₃ or strong Brensted acid of the HA type, where A=BF₄, F₃CSO₃ etc, solvent -benzol, toluene, T=15-30°C.

EFFECT: obtaining palladium cation complexes at one stage, with different anions and high output (90-95%) using of easily accessible reagents.

1 cl, 6 ex, 4 tbl

Description

The invention relates to a method for producing cationic palladium complexes containing organic or organorganic acid acid ligands of the general formula [LPdL ' ₂ ] A, where L is acetylacetonate (Acac), L' are electrically neutral ligands of the type of tertiary phosphines, for example triphenylphosphine, triorthotolylphosphine, triparatolylphosphine, triorthois ., A - anions of type BF ₄ , F ₃ CSO ₃ used as components of catalytic systems in the reaction of selective dimerization of styrene, as well as as catalysts in the reaction of telomerization of isoprene with diethylamino m / Röper M., He R., Schieren M. // Jomal of Molecular Catalysis. 1985. N 31. P.335-345 /.

A known method of producing cationic complexes of palladium / GB 1369128, C07C 2/04; С07С 2/00; (IRS1-7): C07C 3/10; С07С 15/00; С07С 69/76 (1974 / formula [LPdL ' ₂ ] A, where L is π-allyl, consisting in the interaction of halides (X) of palladium type LPdX compounds PR ₃ and AgA, where A is BF ₄ , PF ₆ , SbF ₆ , ClO ₄ .

A known method of producing organometallic complexes / Johnson BFG, Lewis J., White DA // Journal of the Chemical Society. Section A. 1969. N 18. P.5186-5187 / type [LML "] BF ₄ , where L is Acac, L" is cyclooctadiene, M-Pd, Pt consisting in the interaction of acetylacetonato (2-acetylacetonylcyclooct-5-ene -yl) palladium with triphenylmethyl tetrafluoroborate or fluoroboric acid.

The closest analogue of the proposed method is a method for producing cationic palladium complexes of the type [(Acac) Pd (PR ₃ ) ₂ ] BF ₄ / Johnson BFG, Lewis J., White DA // Journal of the Chemical Society. Section A. 1971. N 17. P.2699-2701 /, according to which to the bis (acetylacetonato) palladium, one mole part of triphenylmethyl tetrafluoroborate and then two mole parts of tertiary phosphine are added in dichloromethane. After that, the resulting precipitate was recrystallized from a mixture of solvents dichloromethane-diethyl ether.

Common disadvantages of the known methods are: (1) the multi-stage synthesis process and the need for recrystallization of the final products; (2) the use of expensive starting reagents - silver salts such as AgA, as well as triphenylmethyl tetrafluoroborate.

The objective of the invention is to provide a method that allows to simplify the synthesis of cationic complexes of palladium type [LPdL ' ₂ ] A.

This object is achieved by the fact that in the method for producing cationic palladium complexes containing organic or organorganic acid acid ligands of the general formula [LPdL ' ₂ ] A, where L is acetylacetonate (Acac), L' is tertiary phosphine PR ₃ , where R ₃ is phenyl, possibly substituted, A is an anion of type BF ₄ or F ₃ CSO ₃ , by the interaction of bis (acetylacetonato) palladium, Pd (Acac) ₂ , tertiary phosphine PR ₃ , where R ₃ has the above meaning, and derivatives of boron fluorides in an organic solvent medium, as boron fluoride derivatives use boron trifluoride etherate BF ₃ O Et ₃ or use Bransted HA strong acid, where A = BF ₄ or F ₃ CSO ₃ , and the process is carried out in a medium of benzene or toluene as an organic solvent at a temperature of 15 ÷ 30 ° C.

The method is as follows.

In a three-necked flask in an argon atmosphere, bis (acetylacetonato) palladium, tertiary phosphine, and benzene are successively added. Then, boron trifluoride etherate is added dropwise into the resulting solution with vigorous stirring. The resulting precipitate is filtered off, washed with benzene and dried in vacuum (P = 10 mm Hg, 2 hours, T = 20 ° C).

Example 1. In a three-necked flask at 20 ° C in an argon atmosphere, 1.641 mmol (0.5000 g) of bis (acetylacetonato) palladium, 3.282 mmol of triphenylphosphine, 40 ml of benzene are successively added. Then, 3.282 (0.41 ml) mmol of boron trifluoride etherate is added dropwise into the resulting solution with vigorous stirring. The resulting light yellow precipitate is filtered off, washed with benzene and dried in vacuum (P = 10 mm Hg, 2 hours, T = 20 ° C). Yield 91%. _Mp = 174-176 ° C. The experimental and calculated elemental analysis data are in good agreement (Table 1), ¹ H, ¹⁹ F, ¹³ C, ¹¹ V, ³¹ P NMR spectroscopy data for the complex are presented in Table 2.

Table 1
The results of the elemental analysis of the complex [(Asas) Pd (PPh ₃ ) ₂ ] BF ₄ The elemental composition of the complex [(Asas) Pd (PPh ₃ ) ₂ ] BF ₄ , wt.% Pd FROM N R AT F O Σ Experiment 12.8 61.2 4.24 7.1 1,1 8.25 3.92 98.61 Theor payment 13.0 60.3 4,53 7.6 1.35 9.3 3.92 one hundred

table 2
NMR spectroscopy of the complex [(Acac) Pd (PPh ₃ ) ₂ ] ⁺ BF ₄ ^- . ¹ N ^{13 s 31} P, standard H ₃ PO ₄ Fragment Chem. shifts, ppm Relative intensity Fragment Chem. shifts, ppm Fragment Chem. shifts, ppm -CH ₃ 1,5 6 -CH ₃ 27,551 PPh ₃ 36,359 -CH 5,6 one -CH 102,304 Protons of phenyl rings Band group 7.2-7.8 thirty phenyl rings Band group 128-136 -C = O 188,443

¹⁹ F CCl ₃ F ¹¹ V in MeOH, standard BF ₃ OEt ₂ Fragment Chem. shifts, ppm Fragment Chem. shifts, ppm

In examples 2-4, the reaction is carried out analogously to example 1 with the only difference that other tertiary phosphines are used (see table 3).

Example 5. In a three-necked flask at 20 ° C in an argon atmosphere, 1.641 mmol (0.5000 g) of bis (acetylacetonato) palladium, 1.641 mmol (0.4306 g) of triphenylphosphine, 40 ml of benzene were successively added and allowed to stir for 1 hour, then another 1.641 mmol (0.4306 g) of triphenylphosphine is added to the solution. Then, 1.641 mmol CF ₃ SO ₃ N is added dropwise into the resulting solution with vigorous stirring. The resulting precipitate is filtered off, washed with benzene and dried in vacuum (p = 10 mm Hg, 2 hours, T = 20 ° C). Yield 93%.

Example 6. Similar to example 5, only instead of CF ₃ SO ₃ H used HBF ₄ .

The results of the experiments described in examples 2-6 are summarized in table 3. NMR results of ¹ H spectroscopy of the resulting complexes are presented in table 4.

Thus, the described method allows one step to obtain cationic palladium complexes with various anions of the type [LPdL ' ₂ ] A, with high yields (90-95%), using more affordable reagents.

Claims (1)

A method for producing cationic palladium complexes containing organic or organorganic acid acid ligands of the general formula [LPdL ' ₂ ] A, where L is acetylacetonate (Acac), L' is tertiary phosphine PR ₃ , where R ₃ is phenyl, optionally substituted, A is an anion of type BF ₄ or F ₃ CSO ₃ , by reacting bis (acetylacetonato) palladium, Pd (Acac) ₂ , tertiary phosphine PR ₃ , where R ₃ has the above meaning, and derivatives of boron fluorides in an organic solvent medium, characterized in that as derivatives of boron fluorides use boron trifluoride etherate BF ₃ OEt ₃ or use strong Branstead HA acid, where A is BF ₄ or F ₃ CSO ₃ , and the process is carried out in benzene or toluene as an organic solvent at a temperature of 15–30 ° С.