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Facile Oxidative Addition of C−Cl Bonds to New Neutral and Cationic Rhodium(I)‐Bipyridine Complexes
Author(s) -
Dorta Reto,
Shimon Linda J. W.,
Rozenberg Haim,
Milstein David
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200207)2002:7<1827::aid-ejic1827>3.0.co;2-q
Subject(s) - chemistry , rhodium , cationic polymerization , bipyridine , oxidative addition , oxidative phosphorylation , catalysis , polymer chemistry , combinatorial chemistry , medicinal chemistry , stereochemistry , organic chemistry , crystal structure , biochemistry
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)(C 2 H 4 )] ( 1 ) or directly from [Rh 2 Cl 2 (COE) 4 ] (COE = cyclooctene) in DMSO. The neutral isocyanide complex [RhCl(dmbpy){CNC(CH 3 ) 3 }] ( 4 ) was obtained by reaction of 1 with tert ‐butyl isocyanide. Reaction of dmbpy with [Rh(DMSO) 4 ]PF 6 gave the corresponding cationic complex [Rh(dmbpy)(DMSO) 2 ]PF 6 ( 5 ), and the cationic system [Rh(dmbpy){CNC(CH 3 ) 3 } 2 ]BF 4 ( 6 ) was prepared starting from [Rh(dmbpy)(HD)]BF 4 ( 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 [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 ). The reactivity of 3 towards oxygen led to the isolation of the peroxo Rh III complex [RhCl(O 2 )(dmbpy)(DMSO)] ( 13 ). Complexes 6 , 8 , 9 and 12 were characterized by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)