Facile oxidative addition of C-Cl bonds to new neutral and cationic rhodium(I)-bipyridine complexes

Reto Dorta, Linda J W Shimon, Haim Rozenberg, David Milstein

Research output: Contribution to journalArticle

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Abstract

Neutral and cationic Rh(dmbpy) systems (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized starting from different metal precursors. [RhCl(dmbpy)(DMSO)] (3) was obtained either from the ethylene precursor [RhCl(dmbpy)(C2H4)] (1) or directly from [Rh2Cl2(COE)4] (COE = cyclooctene) in DMSO. The neutral isocyanide complex [RhCl(dmbpy){CNC(CH3)3}] (4) was obtained by reaction of 1 with tert-butyl isocyanide. Reaction of dmbpy with [Rh(DMSO)4]PF6 gave the corresponding cationic complex [Rh(dmbpy)(DMSO)2]PF6 (5), and the cationic system [Rh(dmbpy){CNC(CH3)3}2]BF4 (6) was prepared starting from [Rh(dmbpy)(HD)]BF4 (2) (HD = 1,5-hexadiene). All of these complexes were found to activate the C-Cl bond in benzyl chloride leading to quantitative isolation of the corresponding RhIII complexes [RhCl2(CH2C6H5)(dmbpy)(DMSO)] (7), [RhCl2(CH2C6H5)(dmbpy) {CNC(CH3)3}] (9) [RhCl(CH2-C6H5)(dmbpy)(DMSO)2] PF6 (10) and [RhCl(CH2C6H5)-(dmbpy){CNC (CH3)3}2]BF4 (12). Oxidative addition of dichloromethane by complexes 3 and 5 yielded the corresponding chloromethyl complexes [RhCl2(CH2Cl)(dmbpy)(DMSO)] (8) and [RhCl(CH2Cl)(dmbpy)(DMSO)2]PF6 (11). The reactivity of 3 towards oxygen led to the isolation of the peroxo RhIII complex [RhCl(O2)(dmbpy)(DMSO)] (13). Complexes 6, 8, 9 and 12 were characterized by X-ray crystallography.

Original languageEnglish
Pages (from-to)1827-1834
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number7
Publication statusPublished - 2002

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Rhodium
Dimethyl Sulfoxide
Methylene Chloride
X ray crystallography
Cyanides
Metals
Oxygen

Keywords

  • N ligands
  • Oxidative addition
  • Peroxo complexes
  • Rhodium

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Facile oxidative addition of C-Cl bonds to new neutral and cationic rhodium(I)-bipyridine complexes. / Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Milstein, David.

In: European Journal of Inorganic Chemistry, No. 7, 2002, p. 1827-1834.

Research output: Contribution to journalArticle

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abstract = "Neutral and cationic Rh(dmbpy) systems (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized starting from different metal precursors. [RhCl(dmbpy)(DMSO)] (3) was obtained either from the ethylene precursor [RhCl(dmbpy)(C2H4)] (1) or directly from [Rh2Cl2(COE)4] (COE = cyclooctene) in DMSO. The neutral isocyanide complex [RhCl(dmbpy){CNC(CH3)3}] (4) was obtained by reaction of 1 with tert-butyl isocyanide. Reaction of dmbpy with [Rh(DMSO)4]PF6 gave the corresponding cationic complex [Rh(dmbpy)(DMSO)2]PF6 (5), and the cationic system [Rh(dmbpy){CNC(CH3)3}2]BF4 (6) was prepared starting from [Rh(dmbpy)(HD)]BF4 (2) (HD = 1,5-hexadiene). All of these complexes were found to activate the C-Cl bond in benzyl chloride leading to quantitative isolation of the corresponding RhIII complexes [RhCl2(CH2C6H5)(dmbpy)(DMSO)] (7), [RhCl2(CH2C6H5)(dmbpy) {CNC(CH3)3}] (9) [RhCl(CH2-C6H5)(dmbpy)(DMSO)2] PF6 (10) and [RhCl(CH2C6H5)-(dmbpy){CNC (CH3)3}2]BF4 (12). Oxidative addition of dichloromethane by complexes 3 and 5 yielded the corresponding chloromethyl complexes [RhCl2(CH2Cl)(dmbpy)(DMSO)] (8) and [RhCl(CH2Cl)(dmbpy)(DMSO)2]PF6 (11). The reactivity of 3 towards oxygen led to the isolation of the peroxo RhIII complex [RhCl(O2)(dmbpy)(DMSO)] (13). Complexes 6, 8, 9 and 12 were characterized by X-ray crystallography.",
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T1 - Facile oxidative addition of C-Cl bonds to new neutral and cationic rhodium(I)-bipyridine complexes

AU - Dorta, Reto

AU - Shimon, Linda J W

AU - Rozenberg, Haim

AU - Milstein, David

PY - 2002

Y1 - 2002

N2 - Neutral and cationic Rh(dmbpy) systems (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized starting from different metal precursors. [RhCl(dmbpy)(DMSO)] (3) was obtained either from the ethylene precursor [RhCl(dmbpy)(C2H4)] (1) or directly from [Rh2Cl2(COE)4] (COE = cyclooctene) in DMSO. The neutral isocyanide complex [RhCl(dmbpy){CNC(CH3)3}] (4) was obtained by reaction of 1 with tert-butyl isocyanide. Reaction of dmbpy with [Rh(DMSO)4]PF6 gave the corresponding cationic complex [Rh(dmbpy)(DMSO)2]PF6 (5), and the cationic system [Rh(dmbpy){CNC(CH3)3}2]BF4 (6) was prepared starting from [Rh(dmbpy)(HD)]BF4 (2) (HD = 1,5-hexadiene). All of these complexes were found to activate the C-Cl bond in benzyl chloride leading to quantitative isolation of the corresponding RhIII complexes [RhCl2(CH2C6H5)(dmbpy)(DMSO)] (7), [RhCl2(CH2C6H5)(dmbpy) {CNC(CH3)3}] (9) [RhCl(CH2-C6H5)(dmbpy)(DMSO)2] PF6 (10) and [RhCl(CH2C6H5)-(dmbpy){CNC (CH3)3}2]BF4 (12). Oxidative addition of dichloromethane by complexes 3 and 5 yielded the corresponding chloromethyl complexes [RhCl2(CH2Cl)(dmbpy)(DMSO)] (8) and [RhCl(CH2Cl)(dmbpy)(DMSO)2]PF6 (11). The reactivity of 3 towards oxygen led to the isolation of the peroxo RhIII complex [RhCl(O2)(dmbpy)(DMSO)] (13). Complexes 6, 8, 9 and 12 were characterized by X-ray crystallography.

AB - Neutral and cationic Rh(dmbpy) systems (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized starting from different metal precursors. [RhCl(dmbpy)(DMSO)] (3) was obtained either from the ethylene precursor [RhCl(dmbpy)(C2H4)] (1) or directly from [Rh2Cl2(COE)4] (COE = cyclooctene) in DMSO. The neutral isocyanide complex [RhCl(dmbpy){CNC(CH3)3}] (4) was obtained by reaction of 1 with tert-butyl isocyanide. Reaction of dmbpy with [Rh(DMSO)4]PF6 gave the corresponding cationic complex [Rh(dmbpy)(DMSO)2]PF6 (5), and the cationic system [Rh(dmbpy){CNC(CH3)3}2]BF4 (6) was prepared starting from [Rh(dmbpy)(HD)]BF4 (2) (HD = 1,5-hexadiene). All of these complexes were found to activate the C-Cl bond in benzyl chloride leading to quantitative isolation of the corresponding RhIII complexes [RhCl2(CH2C6H5)(dmbpy)(DMSO)] (7), [RhCl2(CH2C6H5)(dmbpy) {CNC(CH3)3}] (9) [RhCl(CH2-C6H5)(dmbpy)(DMSO)2] PF6 (10) and [RhCl(CH2C6H5)-(dmbpy){CNC (CH3)3}2]BF4 (12). Oxidative addition of dichloromethane by complexes 3 and 5 yielded the corresponding chloromethyl complexes [RhCl2(CH2Cl)(dmbpy)(DMSO)] (8) and [RhCl(CH2Cl)(dmbpy)(DMSO)2]PF6 (11). The reactivity of 3 towards oxygen led to the isolation of the peroxo RhIII complex [RhCl(O2)(dmbpy)(DMSO)] (13). Complexes 6, 8, 9 and 12 were characterized by X-ray crystallography.

KW - N ligands

KW - Oxidative addition

KW - Peroxo complexes

KW - Rhodium

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