Processes involved in the reduction of a cyclometalated palladium(II) complex

Christian M. Frech, Gregory Leitus, David Milstein

Research output: Contribution to journalArticle

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Abstract

Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd {C6H4(CH2PiPr2)}{(C 6H5CH2)PiPr2 }(TFA)] (2). The dinuclear trifluoroacetate complex [Pd(C6H4(CH 2PiPr2)}[TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd(C 6H4(CH2PiPr2)Ji(C 6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2J 2(H)(Cl)] (8), [Pd((C6H5CH2)-P iPr2}2(Cl)2] (4), and both isomeric forms of [Pd(C6H4(CH2PiPr 2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [PdJ(C6H 5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature.

Original languageEnglish
Pages (from-to)894-899
Number of pages6
JournalOrganometallics
Volume27
Issue number5
DOIs
Publication statusPublished - Mar 10 2008

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Palladium
phosphine
palladium
Trifluoroacetic Acid
Hydrochloric Acid
Isomers
hydrochloric acid
phosphines
Metals
Sodium
isomers
sodium
Benzene
dichlorides
metals
sulfides
benzene
routes
methylidyne
room temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Processes involved in the reduction of a cyclometalated palladium(II) complex. / Frech, Christian M.; Leitus, Gregory; Milstein, David.

In: Organometallics, Vol. 27, No. 5, 10.03.2008, p. 894-899.

Research output: Contribution to journalArticle

Frech, Christian M. ; Leitus, Gregory ; Milstein, David. / Processes involved in the reduction of a cyclometalated palladium(II) complex. In: Organometallics. 2008 ; Vol. 27, No. 5. pp. 894-899.
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abstract = "Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd {C6H4(CH2PiPr2)}{(C 6H5CH2)PiPr2 }(TFA)] (2). The dinuclear trifluoroacetate complex [Pd(C6H4(CH 2PiPr2)}[TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd(C 6H4(CH2PiPr2)Ji(C 6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2J 2(H)(Cl)] (8), [Pd((C6H5CH2)-P iPr2}2(Cl)2] (4), and both isomeric forms of [Pd(C6H4(CH2PiPr 2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [PdJ(C6H 5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature.",
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N2 - Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd {C6H4(CH2PiPr2)}{(C 6H5CH2)PiPr2 }(TFA)] (2). The dinuclear trifluoroacetate complex [Pd(C6H4(CH 2PiPr2)}[TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd(C 6H4(CH2PiPr2)Ji(C 6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2J 2(H)(Cl)] (8), [Pd((C6H5CH2)-P iPr2}2(Cl)2] (4), and both isomeric forms of [Pd(C6H4(CH2PiPr 2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [PdJ(C6H 5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature.

AB - Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd {C6H4(CH2PiPr2)}{(C 6H5CH2)PiPr2 }(TFA)] (2). The dinuclear trifluoroacetate complex [Pd(C6H4(CH 2PiPr2)}[TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd(C 6H4(CH2PiPr2)Ji(C 6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2J 2(H)(Cl)] (8), [Pd((C6H5CH2)-P iPr2}2(Cl)2] (4), and both isomeric forms of [Pd(C6H4(CH2PiPr 2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [PdJ(C6H 5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature.

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