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

doi:10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q

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

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

35 Citations (Scopus)

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 Rh^III 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 Rh^III complex [RhCl(O₂)(dmbpy)(DMSO)] (13). Complexes 6, 8, 9 and 12 were characterized by X-ray crystallography.

Original language	English
Pages (from-to)	1827-1834
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Issue number	7
DOIs	https://doi.org/10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q
Publication status	Published - 2002

Keywords

N ligands
Oxidative addition
Peroxo complexes
Rhodium

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q

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@article{dc9c0889ba6c48f38a258d6334027ff9,

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

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.",

keywords = "N ligands, Oxidative addition, Peroxo complexes, Rhodium",

author = "Reto Dorta and Shimon, {Linda J.W.} and Haim Rozenberg and David Milstein",

year = "2002",

doi = "10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q",

language = "English",

pages = "1827--1834",

journal = "Chemische Berichte",

issn = "0009-2940",

publisher = "Wiley-VCH Verlag",

number = "7",

}

TY - JOUR

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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U2 - 10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q

DO - 10.1002/1099-0682(200207)2002:7<1827::AID-EJIC1827>3.0.CO;2-Q

M3 - Article

AN - SCOPUS:0036306067

SP - 1827

EP - 1834

JO - Chemische Berichte

JF - Chemische Berichte

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