Basische metalle

Facile Oxidative Addition of C−Cl Bonds to New Neutral and Cationic Rhodium(I)-Bipyridine Complexes

“…[8] The oxidative addition of carbon halides to low-valent metal complexes is involved in numerous industrially important catalytic cycles and has therefore attracted considerable academic interest. Of particular interest is the activachloride leading to quantitative isolation of the corresponding Rh III complexes [RhCl 2 (CH 2 C 6 H 5 )(dmbpy)(DMSO)] (7), [RhCl 2 (CH 2 C 6 H 5 )(dmbpy){CNC(CH 3 ) 3 }] (9) [RhCl(CH 2 -C 6 H 5 )(dmbpy)(DMSO) 2 ]PF 6 (10) and [RhCl(CH 2 C 6 H 5 )-(dmbpy){CNC(CH 3 ) 3 } 2 ]BF 4 (12). Oxidative addition of dichloromethane by complexes 3 and 5 yielded the corresponding chloromethyl complexes [RhCl 2 (CH 2 Cl)(dmbpy)(DMSO)] (8) and [RhCl(CH 2 Cl)(dmbpy)(DMSO) 2 ]PF 6 (11).…”

Oxidative Addition of Carbon−Chloride Bonds to Rhodium(I) Complexes Containing Terdentate Nitrogen Ligands. X-ray Analyses of Rhodium(I) Chloride and Rhodium(III) Chloromethyl Complexes

“…This is evidenced by the oxidative addition of CH 2 I 2 to [RhCp * (CO) 2 ] (Cp * = pentamethylcyclopentadiene), affording [RhI(CH 2 I)Cp * (CO)], while [RhCp(CO) 2 ] (Cp = cyclopentadiene) in contrast does not react, owing to the smaller electron donor capacity of Cp compared to Cp * − For example, reaction of [Rh(dmpe) 2 ]Cl containing the strongly electron donating Me 2 P(CH 2 ) 2 PMe 2 (dmpe) ligands with CH 2 Cl 2 afforded the complex [RhCl(CH 2 Cl)(dmpe) 2 ]Cl·CH 2 Cl 2 …”

A Novel Route to Formaldehyde and Thioformaldehyde Rhodium Complexes

“…116°C (dec. [4] 5, [22] 6, [32] C [4] [7] 36, [32] and 41, 42 [4] were prepared as described in the 22 3 }I 2 ] (9): A solution of 219.5 mg (0.69 mg (0.25 mmol) of 1 in 5 ml of ethanol was treated with 20.9 mg (0.26 mmol) of CH 3 CO 2 Na and stirred for 15 h at room temp. The mmol) of 6 in 3 ml of benzene was treated dropwise with 85 µl (1.17 mmol) of CH 2 ClI and stirred for 28 h at room temp.…”