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 language | English |
|---|---|
| Pages (from-to) | 1827-1834 |
| Number of pages | 8 |
| Journal | European Journal of Inorganic Chemistry |
| Issue number | 7 |
| Publication status | Published - 2002 |
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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 journal › Article
}
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
UR - http://www.scopus.com/inward/record.url?scp=0036306067&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0036306067&partnerID=8YFLogxK
M3 - Article
SP - 1827
EP - 1834
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 7
ER -